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You are on page 1of 285

VOLUME 47

Editors

BENJAMIN BEDERSON

New York University

New York, New York

HERBERT WALTHER

Max-Plank-Institut für Quantenoptik

Garching bei München

Germany

Editorial Board

P. R. BERMAN

University of Michigan

Ann Arbor, Michigan

M. GAVRILA

F. O. M. Institut voor Atoom-en Molecuulfysica

Amsterdam, The Netherlands

M. INOKUTI

Argonne National Laboratory

Argonne, Illinois

W. D. PHILIPS

National Institute for Standards and Technology

Gaithersburg, Maryland

Founding Editor

SIR DAVID BATES

Supplements

1. Atoms in Intense Laser Fields, Mihai Gavrila, Ed.

2. Cavity Quantum Electrodynamics, Paul R. Berman, Ed.

3. Cross Section Data, Mitio Inokuti, Ed.

ADVANCES IN

ATOMIC,

MOLECULAR,

AND OPTICAL

PHYSICS

Edited by

Benjamin Bederson

DEPARTMENT OF PHYSICS

NEW YORK UNIVERSITY

NEW YORK, NEW YORK

Herbert Walther

UNIVERSITY OF MUNICH AND

MAX-PLANK INSTITUT FÜR QUANTENOPTIK

MUNICH, GERMANY

Volume 47

Boston London Sydney Tokyo

This book is printed on acid-free paper.

∞

Copyright

C 2001 by ACADEMIC PRESS

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01 02 03 04 05 06 SB 9 8 7 6 5 4 3 2 1

Contents

CONTRIBUTORS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . vii

P. Meystre

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

II. s-Wave Scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

III. A Microreview of Manybody Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

IV. Mean-Field Theory of Bose–Einstein Condensates . . . . . . . . . . . . . . . . . . 14

V. Four-Wave Mixing of de Broglie Waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

VI. Mixing of Optical and Matter Waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37

VII. Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

VIII. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

Photoassociation in a Gas of Laser-Cooled Atoms

Françoise Masnou-Seeuws and Pierre Pillet

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

II. Physical Concepts in Photoassociation and Formation of Molecules . . 57

III. Ultracold Molecule Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80

IV. Theoretical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100

V. Present Status of the Comparison between Experiment and Theory:

Formation Rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109

VI. New Schemes for Making Ultracold Molecules . . . . . . . . . . . . . . . . . . . . . . 116

VII. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117

VIII. Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120

IX. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120

and Comets: Needs for Spectroscopic and Collision Data

Yukikazu Itikawa, Sang Joon Kim, Yong Ha Kim, and Y. C. Minh

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130

II. Spectroscopy of the Giant Planets: Needs for Spectroscopic

and Collision Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131

III. Spectroscopy of Comets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145

IV. Spectral Databases and Improvements Needed . . . . . . . . . . . . . . . . . . . . . . 155

V. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157

VI. Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157

VII. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157

v

vi Contents

Spectroscopy with Laser Probing of the Excited State

Andrew James Murray and Peter Hammond

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163

II. Atomic Deflection Using Electron Impact . . . . . . . . . . . . . . . . . . . . . . . . . . . 167

III. Doubly Excited States Studied via the Fluorescence Decay Product:

Recoiling Excited Atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182

IV. Stepwise Laser Probing of Deflected Metastable Targets . . . . . . . . . . . . . 187

V. Conclusions and Future Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199

VI. Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201

VII. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202

J. P. Woerdman, N. J. van Druten, and M. P. van Exter

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205

II. Overview of Threshold Behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207

III. Good-Cavity versus Bad-Cavity Regime . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211

IV. Spontaneous Emission Factor β . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214

V. Cavity QED and β . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219

VI. Magnitude of β . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221

VII. Relaxation Oscillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222

VIII. Disappearance of Fluctuation Threshold . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227

IX. Petermann Excess Quantum Noise . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236

X. Finite Number of Atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242

XI. Concluding Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244

XII. Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246

XIII. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246

SUBJECT INDEX . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249

CONTENTS OF VOLUMES IN THIS SERIES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261

Contributors

Numbers in parentheses indicate the pages on which the authors’ contributors begin.

Nedlands, Perth WA6907, Australia

YUKIKAZU ITIKAWA (129), Institute of Space and Astronomical Science, 3-1-1

Yoshinodai, Sagamihara 229-8510, Japan

SANG JOON KIM (129), Department of Astronomy and Space Science, Kyung Hee

University, Suwon, 449-701, Korea

YONG HA KIM (129), Department of Astronomy and Space Science, Choong Nam

National University, Daejeon, 305-764, Korea

FRANÇOISE MASNOU-SEEUWS (53), Laboratoire Aimé Cotton, Bât. 505, Campus

d’Orsay, 91405 Orsay Cedex, France

P. MEYSTRE (1), Optical Sciences Center, The University of Arizona, Tucson,

AZ 85721

Y. C. MINH (129), Korea Astronomy Observatory, Hwaam, Yusong, Daejeon,

305-348, Korea

ANDREW JAMES MURRAY (163), Department of Physics and Astronomy, The

University of Manchester, Manchester M13 9PL, United Kingdom

PIERRE PILLET (53), Laboratoire Aimé Cotton, Bât. 505, Campus d’Orsay, 91405

Orsay Cedex, France

N. J. VAN DRUTEN (205), Department of Applied Physics, Delft University of

Technology, Lorentzweg 1, 2628 CJ Delft, The Netherlands

M. P. VAN EXTER (205), Huygens Laboratory, Leiden University, 2300 RA Leiden,

The Netherlands

J. P. WOERDMAN (205), Huygens Laboratory, Leiden University, 2300 RA Leiden,

The Netherlands

vii

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Advances in

VOLUME 47

This Page Intentionally Left Blank

ADVANCES IN ATOMIC, MOLECULAR, AND OPTICAL PHYSICS, VOL. 47

NONLINEAR OPTICS

OF DE BROGLIE WAVES

P. MEYSTRE

Optical Sciences Center, The University of Arizona, Tucson, Arizona 85721

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

II. s-Wave Scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

III. A Microreview of Manybody Theory . . . . . . . . . . . . . . . . . . . . . . . . . . 8

IV. Mean-Field Theory of Bose–Einstein Condensates . . . . . . . . . . . . . . . . . 14

A. Zero Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

B. Finite Temperatures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

V. Four-Wave Mixing of de Broglie Waves . . . . . . . . . . . . . . . . . . . . . . . . 22

A. Mean-Field Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

B. Quantum Theory of Atomic Four-Wave Mixing . . . . . . . . . . . . . . . . . 27

VI. Mixing of Optical and Matter Waves . . . . . . . . . . . . . . . . . . . . . . . . . . 37

A. Parametric Amplification of Atomic and Optical Fields . . . . . . . . . . . . 38

B. Matter-Wave Superradiance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

C. Phase-Coherent Matter-Wave Amplification . . . . . . . . . . . . . . . . . . . 49

VII. Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

VIII. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

I. Introduction

One of the most profound revolutions brought about by quantum mechanics is that

it does away with the distinction between particles and waves. Planck and Einstein

first postulated the existence of light quanta to explain the blackbody radiation

spectrum and the photoelectric effect. They argued that one should associate to

the light quantum an energy E = hω and a momentum p = hk. Shortly thereafter,

de Broglie went one step further and proposed that electrons, and for that matter

all massive particles, should be thought of as waves of energy E = h 2 q 2 /2M and

wavelength = h/q, where q is the particle momentum [1].

One relatively recent application of these developments is atom optics. Its ex-

perimental foundations were laid as early as 1929, when O. Stern et al. demon-

strated the reflection and diffraction of atoms from metallic and crystalline surfaces

[2, 3]. A few years later, Frisch measured the deflection of atoms as a result of

absorption of light followed by spontaneous emission [4]. Atom optics is now an

important subfield of atomic, molecular and optical physics, and many passive

atom-optical elements, including mirrors, lenses, gratings, interferometers and

resonators, have been demonstrated.

All rights of reproduction in any form reserved.

ISBN 0-12-003847-1/ISSN 1049-250X/01 $35.00

2 P. Meystre

Just as the invention of the laser lead to a profound revolution in optics, and

enabled the development of nonlinear optics and quantum optics, a similar revo-

lution is taking place in atom optics now that experimentalists can more or less

routinely generate Bose–Einstein condensates. By extracting “atom laser” beams

from these condensates, it has been possible to carry out the first nonlinear atom

optics and quantum atom optics experiments. These are the developments reviewed

in this chapter.

The early experiments in atom optics considered low-density atomic samples,

where the atoms in the light fields evolve independently from each other. How-

ever, when the sample densities or atomic beam fluxes become large enough that

atom–atom interactions become important, the dynamics of a given atom become

dependent on the presence of other atoms. In traditional atomic physics, atom–

atom interactions are described as collisions. The point of view adopted in non-

linear atom optics [5–8] is different. One considers instead these interactions as a

mechanism that allows matter waves to interact and mix, very much like optical

waves in nonlinear optics [9–13].

The analogy between nonlinear optics and nonlinear atom optics is actually

quite profound: in conventional optics, effective nonlinear equations for the op-

tical fields follow from the elimination of the medium dynamics, while in atom

optics nonlinear matter-wave dynamics results from collisions, which are in turn

effective manybody interactions resulting from the (partial) elimination of the

electromagnetic field.

The goal of this chapter is to review the foundations and some of the recent de-

velopments of nonlinear atom optics, concentrating on the case of bosonic atoms.

Section II briefly discusses s-wave scattering, which provides an appropriate

description of the low-energy collisions of relevance in ultracold, low-density

samples of bosonic atoms. As such, this analysis determines the properties of

the nonlinearity most commonly used in the nonlinear manipulation of bosonic

Schrödinger fields. We then turn to a microreview of the formalism of manybody

theory, which allows one to treat atomic samples as fields, in close analogy to the op-

tical case. Section IV introduces the mean-field theory appropriate for the descrip-

tion of ultracold atomic samples, leading to the famous Gross–Pitaevskii equation

widely used in the dynamical description of Bose–Einstein condensates at zero tem-

perature. We also discuss ways to improve on this approach at finite temperatures.

With this formalism at hand, Sect. V discusses matter-wave four-wave mixing

in low-density atomic condensates both in a mean-field approach and in the frame-

work of a quantum optics-like description that analyzes the buildup of the side

modes from noise fully quantum mechanically.

Finally, the last section of this review turns to the nonlinear mixing between

optical and matter waves, giving in particular an analysis of “matter-wave super-

radiance” and of phase-coherent matter wave amplification.

To keep this review of a reasonable size, we have chosen to limit the discussion

to those aspects of nonlinear atom optics that have already received experimental

NONLINEAR OPTICS OF DE BROGLIE WAVES 3

confirmation. We have also ignored the fascinating aspects related to the generation

of matter-wave solitons, which is the topic of another review [14]. A considerably

more detailed presentation of this material can be found in a monograph, Atom

Optics, by P. Meystre, to be published by Springer-Verlag (2001).

In low-density samples of ultracold bosonic atoms, the dominant source of colli-

sions is in the form of ground-state two-body interactions, which can be treated

relatively simply in the shapeless, or s-wave scattering approximation. The pur-

pose of this section is to review some key aspects of these collisions in the simplest

possible way. This leads to the concept of scattering length, which allows us to

describe them in terms of a single parameter. Since this problem is treated at great

length in many quantum mechanics texts, we merely outline the essential steps

here.

We proceed by describing the elastic scattering between two particles of masses

M1 and M2 in the partial waves formalism [15–19]. Introducing a coordinate system

in which the center of mass of the two-particle system is at rest, this problem

reduces to the scattering of a particle of reduced mass,

M1 M2

μ= (1)

M1 + M2

U (r) = U (r ). (2)

We consider a situation where the incident wave is a plane wave, while the outgoing

wave is asymptotically a spherical wave, that is,

eikr

ψ(r) ≃ eikz + f k (θ, φ) , (3)

r

incident wave, it depends in general on the spherical coordinates θ and φ defining

the direction in which the particle is scattered. The particle current,

−i h ∗

j= [ψ ∇ψ − (∇ψ ∗ )ψ], (4)

2μ

4 P. Meystre

is equal to

hk

ji = (5)

μ

hk

jo (r, θ, φ) ≃ | f k (θ, φ)|2 (6)

μr 2

for the outgoing wave.1 Consequently, the differential cross section is related to

the scattering amplitude by

dσ (θ, φ)

= | f k (θ, φ)|2 . (7)

d

for the relative atomic motion in terms of partial waves,

1

φk,l,m (r) = u k,l (r )Ylm (θ, φ), (8)

r

− 2

+ 2

+ U (r ) u k,l (r ) = u k,l (r ), (9)

2μ dr 2μr 2μ

with u k,l (r = 0) = 0, and the Ylm (θ, φ) are spherical harmonics. For large r, one

can neglect both the effects of the central potential U (r ) and of the centrifugal

potential l(l + 1)h 2 /2μr 2 , so that

d2

2

+ k u k,l (r ) ≃ 0, (10)

dr 2

and

lπ

u k,l (r )|r →∞ ∝ sin kr − + δl . (11)

2

1

This approximate value takes into account the fact that while the r component of jo scales as

1/r 2 , its θ and φ components scale as 1/r 3 , since, as we recall, (∇)r = ∂/∂r, (∇)θ = (1/r )(∂/∂θ) and

(∇)φ = (1/r sin θ)(∂/∂φ). Hence they are negligible in the asymptotic region r → ∞.

NONLINEAR OPTICS OF DE BROGLIE WAVES 5

that u k,l → 0 as r → 0, the term lπ/2 being included explicitly to account for

the fact that in the free-particle case U (r ) = 0 the phase of u k,l (r ) equals lπ /2. In

other words, the phase δl is taken relative to the zero-potential solution. It is easily

shown that 2δl may be interpreted as the phase accumulated by the outgoing wave

relative to that of a free outgoing wave; see, e.g., [19].

We now expand the wave function (3) in terms of the partial waves (8), taking

advantage of the fact that for elastic collisions the final energy h 2 k 2 /2μ is the

same as the incident energy. We note in addition that for a central potential the

scattering wave function must be symmetric under rotations about the direction of

incidence of the incoming particle, the z axis. Hence, we need only include partial

waves of fixed momentum k and with m = 0, so that f k (θ, φ) → f k (θ) and

∞

ψ(r) = Cl φk,l,0 (r). (12)

l=0

The coefficients Cl can be determined from the requirement that the asymptotic

limit of this expansion is of the form (3). Noting that from Eqs. (8) and (11) we

have for r → ∞,

φk,l,0 (r) ≃ Yl (θ), (13)

2ir

and using the expansion of the plane wave exp(ikz) in terms of spherical harmonics,

∞

eikz = i l 4π (2l + 1) jl (kr )Yl0 (θ)

l=0

∞

1 lπ

≃ i l 4π (2l + 1) sin kr − Yl0 (θ), (14)

l=0

kr 2

where we have used the asymptotic expansion of the spherical Bessel functions

jl (kr ) in the second line [19]. This requirement leads after some algebra to the

partial waves expansion of the scattering amplitude f k (θ) as

∞ ∞

1

f k (θ) = f k,l (θ) = 4π(2l + 1)eiδl sin δl Yl0 (θ). (15)

l=0

k l=0

We have seen in Eq. (7) that the differential scattering cross section is simply given

by | f k (θ )|2 . The total scattering cross section σ is obtained by integrating this

6 P. Meystre

d Yl0∗ 0

′ (θ)Yl (θ) = δl,l ′ , (16)

∞

4π

σ = (2l + 1) sin2 δl . (17)

k 2 l=0

For the ultracold applications of atom optics that we have in mind, we can

restrict the analysis to the case of particles of such low energy that

kr0 ≪ 1, (18)

where r0 is the range of the potential U (r ). As it turns out, the dominant partial

wave in the vicinity of the potential U (r ) is then the s-wave, ℓ = 0 [17].

We can gain an intuitive feeling for this important property by returning to the

expansion (14) in terms of spherical harmonics. More specifically, consider first a

free spherical wave,

(0) 2k 2

φk,l,m (r) = jl (kr )Ylm (θ, φ), (19)

π

where the jl are spherical Bessel functions. The associated probability for the

particle to be in the solid angle d about θ0 and φ0 and between r and r + dr is

(0)

2

Pl (θ0 ,φ0 ) ∝ r 2

φk,l,m (r)

dr d . (20)

For ultracold particles, kr → 0, the Bessel functions take the asymptotic form

(kr )l

jl (kr ) ≃ , (21)

(2l + 1)!!

and it can be shown that the function K 2r 2 jl2 (kr ) is negligible for

l(l + 1) > kr. (22)

(0)

The expansion (14) of a plane wave into free spherical waves φk,l,m (r) leads

therefore to the following physical interpretation: in the range r < r0 of U (r )

and for momenta k small enough that kr0 ≪ 1, the incident plane wave acts for all

NONLINEAR OPTICS OF DE BROGLIE WAVES 7

tum, it must be scattered into another spherical wave. In other words, for particles

of sufficiently low energy, kr0 → 0, one needs consider only the partial wave

of angular momentum l = 0 in Eq. (17). This is the so-called s-wave scattering

approximation, which yields the cross section

4π

σ ≃ sin2 δ0 . (23)

k2

It can be shown [18] that in the low-energy regime, one has approximately

0

which

√ is much smaller than unity since kr0 ≪ 1. In that case, and with Y0 (θ, φ) =

1/ 4π Eq. (15) gives

δ0

f k,0 ≃ , (25)

k

σ = 4πa 2 , (26)

δ0

a ≡ − f = −lim . (27)

k→0 k

Physically, the scattering length can be obtained by solving the radial wave equation

d2

− U (r ) u(r ) = 0, (28)

dr 2

the length a corresponding to the point where the asymptote of u(r ) intersects

the horizontal axis. In case of a hard-sphere potential of radius r0 , it corresponds

to that radius, a = r0 . In general, the scattering length may be either positive

or negative. Positive scattering lengths correspond to repulsive interactions, and

negative scattering lengths to attractive interactions.

To conclude this section, we note that it is often possible to replace the two-body

potential U (r ) by a pseudo-potential that gives the same scattering length as the

real potential and yielding the same s-wave scattering solutions. For unperturbed

8 P. Meystre

4πah 2

U (r ) = δ(r ). (29)

M

Very much as nonlinear optics is advantageously described in terms of Maxwell

fields, rather than in the particle (photon) picture, nonlinear atom optics is best

analyzed in terms of Schrödinger fields rather than single-atom dynamics. To

fully set the stage for our discussion, we therefore still need to introduce some key

elements of the formalism of second quantization. While certainly not necessary in

principle, this approach permits one to draw considerable intuition and inspiration

from traditional nonlinear optics. Additionally, the introduction of particle creation

and annihilation operators and of a Fock space for particles allows one to easily

account for systems where the total number of particles in a given mode is not

conserved. Finally, the inclusion of the quantum statistics of the particles proceeds

in a particularly simple way.

Second quantization finds its origin in the desire to treat the dynamics of N

identical particles satisfying either bosonic or fermionic statistics. One approach to

this problem consists in considering the N-particle wave function φ(r1 , . . . , r N , t),

evolving according to the N-particle Hamiltonian

N

HN = Hi , (30)

i=1

either symmetric or antisymmetric under particle exchange, depending on the par-

ticles being bosons or fermions. Alternatively, one can describe this same problem

more conveniently using the field-theoretical approach of second quantization

[20–22].

It is far beyond the scope of this review to give a rigorous treatment of second

quantization starting from a canonical quantization approach. Rather, we postulate

that the Schrödinger wave function ψ(r) becomes an operator (r) ˆ which, for

bosonic particles, satisfies the commutation relations

ˆ

[(r), ˆ † (r′ )] = δ(r − r′ ),

(31)

ˆ

[(r), ˆ )] = 0,

(r ′

(32)

NONLINEAR OPTICS OF DE BROGLIE WAVES 9

ˆ

[(r), ˆ † (r′ )]+ = δ(r − r′ ),

(33)

ˆ

[(r), ˆ ′ )]+ = 0.

(r (34)

ˆ

shall see, (r) may be interpreted as an operator annihilating a particle at position

r and ˆ † (r) creates a particle at location r. The second-quantized Hamiltonian

corresponding to the single-particle Hamiltonian H = −h 2 ∇ 2 /2M + V (r) is

2

H= ˆ † (r) − h ∇ 2 + V (r) (r).

d 3r ˆ (35)

2M

Physically, one can understand this Hamiltonian in the following way: the field

ˆ

operator (r) picks a particle at location r, the Hamiltonian evolution H =

−h 2 ∇ 2 /2M is applied to this particle, and the operator ˆ † (r) puts it back into

place. Finally, the integral in Eq. (35) guarantees that all particles in the ensemble

are subject to this treatment.

From this Hamiltonian, it is easy to find the Heisenberg equation of motion for

ˆ

the field operator (r). For the case of bosons, we have

ˆ

d (r, t)

ih ˆ

= [(r, t), H]

dt

2

ˆ

= d 3r ′ (r, ˆ † (r′ , t) − h ∇ 2 + V (r′ ) (r

t), ˆ ′ , t)

2M

2

h ˆ

= − ∇ 2 + V (r) (r, t), (36)

2M

where we have used the relation [A, BC] = B[A, C] + [A, B]C and the commuta-

tion relations (33) and (34). It is easily seen that the same result holds for fermions,

despite the different commutation relations. Hence, the Heisenberg equation of mo-

ˆ

tion for the Schrödinger field operator (r, t) has the same form as the Schrödinger

equation for the wave function ψ(r, t) in usual quantum mechanics. We can think

ˆ

of the operator (r, t) as the quantized form of the single-particle Schrödinger

field ψ(r, t), in much the same way as we have quantized the electromagnetic

field, E(r, t) → Ê(r, t). Note, however, that while the quantization of the electro-

magnetic field leads to new physics, such is not the case for second quantization,

when applied to the nonrelativistic problems that we address here. It is merely a

convenient bookkeeping tool.

10 P. Meystre

function φ N (r1 , . . . r N , t) is

1

|φ N
= √ ˆ † (r N ) . . .

d 3r1 . . . d 3r N φ N (r1 , . . . , r N , t) ˆ † (r1 )|0
, (37)

N!

ˆ

(r)|0
= 0. (38)

N̂ ≡ ˆ † (r)(r)

d 3r ˆ (39)

N

[A, B N . . . B1 ] = B N . . . Bi+1 [A, Bi ]Bi−1 . . . B1 , (40)

i=1

N̂ |φ N = N |φ N . (41)

ˆ N ˆ † (r N −1 ) . . .

ˆ † (r1 )|0 .

(r)|φ N = √ d 3r1 . . . d 3r N −1 φ N (r1 , . . . r N −1 , t)

N!

(42)

tional quantum mechanical description of the N-body problem in terms of the

sum of N individual Hamiltonians can be demonstrated by applying the manybody

Hamiltonian (35) to the N-particle state |φ N , showing that

1

H|φ N
= √ d 3 r d 3 r1 . . . d 3 r N ˆ

ˆ † (r)H (r)(r)

N!

× φ N (r1 , . . . r N )ˆ † (r N ) . . .

ˆ † (r1 )|0

N

1

= √ d 3 r1 . . . d 3 r N ˆ † (r N ) . . .

ˆ † (r1 )|0
Hi φ(r1 . . . r N ),

N ! i=1

(43)

NONLINEAR OPTICS OF DE BROGLIE WAVES 11

where

h2 2

Hi ≡ − ∇ + V (ri ). (44)

2M i

This result shows that the multiparticle evolution governed by the Schrödinger

equation of motion

d

ih φ N (r1 , . . . r N , t) = HN φ N (r1 , . . . r N , t) (45)

dt

d |φ N

ih = H |φ N
. (46)

dt

This equivalence is a direct consequence of the fact that the Schrödinger field

operator evolution is governed by the single-particle Hamiltonian H; see Eq. (36).

It is easily shown that the Schrödinger field operator satisfies a conservation of

probability law. Introducing the density

ˆ † (r, t)(r,

n̂(r, t) = ˆ t)

d n̂(r, t) ˆ † (r, t)

d ˆ

= ˆ

(r, t) + ˆ † (r, t) d (r, t)

dt dt dt

−i h ˆ † (r, t))(r,

ˆ ˆ † (r, t)∇ 2 (r,

ˆ

= [(∇ 2 t) − t)] = −∇ · ĵ, (47)

2M

−i h

ˆ † (r, t)∇ (r,

ˆ ˆ † (r, t)](r,

ˆ

ĵ ≡ t) − [∇ t) , (48)

2M

Very much as it is useful in optics to introduce a mode expansion of the electric

field operator E(r, t), we can introduce a mode expansion of the Schrödinger field

operator. We illustrate how this works by expanding (r, ˆ t) on the orthonormal

eigenfunctions ϕn (r) of the time-independent Schrödinger equation,

h2 2

− ∇ + V (r) ϕn (r) = E n ϕn (r)

2M

12 P. Meystre

as

ˆ

(r, t) = ϕn (r)ĉn (t), (49)

n

where the mode label n stands for the complete set of quantum numbers necessary

to characterize that mode. Inserting this expression and its hermitian conjugate

into the second-quantized Hamiltonian (35) gives

H= E n ĉn† ĉn , (50)

n

d 3r ϕn∗ (r)ϕm (r) = δnm (51)

and have also assumed a discrete energy spectrum for simplicity. With Eq. (51) we

can express the operators ĉn from Eq. (49) as

ĉn (t) = ˆ

d 3r ϕn∗ (r)(r, t). (52)

For the bosonic commutation relations (31) and (32), this gives

†

[ĉn , ĉm ] = δnm ,

(53)

[ĉn , ĉm ] = 0,

fermionic particles one finds

†

[ĉn , ĉm ]+ = δnm ,

(54)

[ĉn , ĉm ]+ = 0.

The combination of the second-quantized Hamiltonian (50) and the bosonic com-

mutation relations (53) shows that in that case, we have reduced the problem

to that of a set of harmonic oscillators of energies E n . We can therefore inter-

†

pret ĉn as an annihilation operator, and ĉn as a creation operator for mode n,

NONLINEAR OPTICS OF DE BROGLIE WAVES 13

with

√

ĉn |Nn
= N n |Nn − 1
,

† √

ĉn |Nn
= Nn + 1|Nn + 1
, (55)

†

ĉn ĉn |Nn
= Nn |Nn
,

where Nn is the number of particles in the mode. This shows that in second quan-

tization, the state of the system is simply expressed in terms of the number of

excitations of each single-particle mode. The total number of particles in the

system is given by

N̂ = N̂ n = ĉn† ĉn = ˆ † (r)(r),

d 3r ˆ (56)

n n

and is clearly a constant of motion for the Hamiltonian (50). Likewise, the indi-

vidual populations of all modes of the matter field are also constants of motion.

This latter property ceases to hold, however, as soon as interactions are permitted,

e.g., in the presence of a light field.

In case the matter–light coupling is via the electric dipole interaction, the

second-quantized interaction Hamiltonian is bilinear in the optical field creation

and annihilation operators, but quadratic in matter-field creation and annihilation

operators, a direct consequence of the conservation of the total number of particles

N̂ . An example of such an interaction Hamiltonian is

lated” from state m and “created” state n.

As is the case for the simple harmonic oscillator, nothing prevents us from

putting as many bosons in mode n as we wish. This, however, is no longer the case

for fermions: this is apparent from the anticommutation relation [ĉn , ĉm ]+ = 0,

† †

which for m = n yields ĉm ĉm = ĉm ĉm = 0. This indicates that the ground state of

a given mode is reached at the latest once a single particle has been removed. It is

furthermore impossible to populate a given mode with more than one particle, a

property further evidenced by the fact that the number operator N̂ n and its square

N̂ 2n are easily shown to be equal,

N̂ 2n = N̂ n .

Hence the population of a given mode must be either zero or one. In addition, one

14 P. Meystre

†

where |0
is the vacuum state (absence of particle), indicating that ĉn |0
is an

eigenstate of mode n with value 1. This is nothing but Pauli’s exclusion principle,

expressed in the formalism of second quantization in terms of anticommutator

relations.

In the framework of second quantization, two-body collisions characterized by

the interaction energy V (ri , r j ) are described by the Hamiltonian

1

V= ˆ † (r)

d 3r d 3r ′ ˆ † (r′ )V (r, r′ )(r

ˆ ′ )(r),

ˆ (58)

2

ˆ ′ )(r)

the operator (r ˆ picking two particles at locations r and r′, to which the

two-body Hamiltonian V (r, r′ ) is applied before they are put back into place. The

application of V on the state vector |φ N
gives

N N

1

V|φ N
= √ × d 3r1 · · · d 3r N V (ri , r j )

N ! i=1 j>i

ˆ † (r N ) . . .

× φ N (r1 , . . . , r N ) ˆ † (r1 )|0
. (59)

One often encounters situations where the scalar Schrödinger field we have

considered so far needs to be extended to a multicomponent field, to account for

the internal states of the atoms involved. The generalization of the formalism of

second quantization to this case is straightforward.

A. ZERO TEMPERATURE

At zero temperature, a trapped Bose–Einstein condensate is characterized by the

property that all atoms occupy the same quantum state. In the absence of atom–

atom interaction, this is the ground state of the trap, but collisions change this

property somewhat, a point to which we return shortly. In this section, we derive

an effective nonlinear equation that describes the dynamics of such a condensate,

the so-called Gross–Pitaevskii equation [23–25]. We first use it to determine the

ground state of the system, and then extend the analysis to discuss the elementary

excitations of the condensate. This will give us a first peek at the profound analogy

NONLINEAR OPTICS OF DE BROGLIE WAVES 15

between nonlinear optics and nonlinear atom optics. A considerably more de-

tailed theoretical discussion of Bose–Einstein condensation of low-density atomic

systems can be found in the review by Dalfovo et al. [26].

There are several ways to derive the Gross–Pitaevskii equation. For example, the

Hartree mean-field approach consists of factorizing the N-particle wave function

φ N (r1 , . . . r N ) of Eq. (37) as

rN

φ N (r1 , . . . r N ) = ϕ N (r), (60)

r=r1

the so-called time-dependent Hartree approximation, the equations of motion for

these wave functions, also called Hartree wave functions, are determined from the

Hartree variational principle [27, 28],

δ ∂

= φ N |i h − H|φ N = 0. (61)

δϕ N∗ (r) ∂t

this readily yields

∂ϕ N (r)

ih = H ϕ N (r) + (N − 1) d 3r ′ V (r, r′ )ϕ N∗ (r)ϕ N2 (r′ ) (62)

∂t

The (N − 1) factor appearing in this expression results from the fact that the two-

body Hamiltonian V involves two creation operators on the left of V ; see Eq. (58).

This leads to N (N − 1) equivalent terms, while the single-particle Hamiltonian,

which involves only one annihilation operator on the left of H, leads to N equivalent

terms.

Alternatively, one can describe the condensate in the context of another mean-

field theory whose basic ingredient consists in separating out the condensate con-

tribution from the Schrödinger field operator ˆ † (r) and treating it as a number,

the order parameter, or condensate wave function (r, t). Specifically, we assume

that

ˆ

(r, ˆ ′ (r, t),

t) = (r, t) + (63)

where

16 P. Meystre

phase as a result of spontaneous symmetry breaking. While this is a conve-

nient and expeditious way to derive important results, we note that this assump-

tion is not needed in general. We also remark that in the thermodynamic limit

N → ∞ at constant density, this and the Hartree approach can be shown to be

equivalent.

ˆ ′ (r, t), which measures the departure of the condensate

Clearly, the operator

state from its mean-field value, must satisfy the Bose commutation relation

ˆ ′ (r, t),

[ ˆ ′† (r′ , t)] = δ(r − r′ ). (65)

The dynamics of the condensate wave function (r, t) can be obtained by taking

the expectation value of the Heisenberg equation of motion for the field operator

ˆ

(r, t). We have seen in Sect. II that in the case of s-wave scattering the two-body

potential can be approximated by the local interaction

V (r − r′ ) = gδ(r − r′ ), (66)

where

4π h 2 a

g= (67)

M

and a is the s-wave scattering length. In that case, we obtain the Gross-Pitaevskii

nonlinear Schrödinger equation [23–25],

h2 2

∂

ih (r, t) = − ∇ + Vtrap (r) + g|(r, t)|2 (r, t). (68)

∂t 2M

ˆ † (r, t)(r,

ˆ ˆ

t)(r, ˆ † (r, t)
(r,

t)
= ˆ ˆ

t)
(r, t)
. (69)

In addition to the familiar contributions of the kinetic energy and the trap

potential, the Gross–Pitaevskii equation contains an additional energy term,

g|(r, t)|2 (r, t), proportional to the local density |(r, t)|2 of the condensate.

This term is referred to as (twice) the mean-field energy of the condensate. It plays

a fundamental role in its dynamics. Most important in the context of this review,

the formal analogy between this term and the contribution of a local Kerr nonlin-

earity in optics suggests that the atom–atom interactions that are at its origin play

a role similar to that of a nonlinear medium for light. It is this observation which

NONLINEAR OPTICS OF DE BROGLIE WAVES 17

opens up the way to nonlinear atom optical effects [5, 29, 30] and wave mixing

phenomena in Bose–Einstein condensates.

The fact that g|(r, t)|2 (r, t) is twice the mean-field energy results from

the observation that a Gross–Pitaevskii equation may also be obtained from the

Hartree-type variational principle,

∂ϕ(r, t) δE

ih = ∗ , (70)

∂t δϕ (r, t)

h2

g

E[ϕ] = d 3r |∇ϕ|2 + Vtrap |ϕ|2 + |ϕ|4 , (71)

2M 2

and ϕ(r, t) is the Hartree condensate wave function. This allows us to identify the

mean-field energy as

g

E mf = |ϕ(r, t)|2 . (72)

2

wave function as

where μ is the chemical potential and the normalization of (r), taken to be real

for now, is

d 3r 2 (r) = N , (74)

N being the number of particles in the condensate. Substituting Eq. (73) into the

Gross–Pitaevskii equation (4) gives

h2 2

μ(r) = − ∇ + Vtrap (r) + g|(r, t)|2 (r). (75)

2M

With the normalization condition (74), this yields immediately the expression

1

μ= E kin + E pot + 2E mf . (76)

N

18 P. Meystre

In the limit of large condensates, the mean-field contribution dominates over the

kinetic energy term,2 except near the condensate boundary. In that case, one can

neglect that latter term, the so-called Thomas–Fermi approximation. Equation (75)

becomes then simply

1

|(r)|2 = (μ − Vtrap ) (78)

g

for μ > Vtrap (r) and 0 otherwise. This discontinuity in the density profile is an

artifact of the Thomas-Fermi approximation, which is removed when taking the

quantum pressure properly into account.

So far, we have concentrated on the static properties of the condensate ground

state. The analysis of small perturbations away from that state can be performed

using a Bogoliubov quasi-particle approach [20, 31–33]. For trapped particles, it is

useful to work in coordinate space instead of the perhaps more familiar momentum

representation. We proceed by expressing the Schrödinger field as

†

ˆ

(r, t) = (r) + [u j (r)α̂ j (t) + v ∗j (r)α̂ j (t)], (79)

j>0

ulation No ≫ 1 of the ground-state mode j = 0, and the quantum numbers j label

elementary excitations above the condensate state. The quasi-particle operators

†

α̂ j (t) are required to satisfy the bosonic commutation relations [α̂ j , α̂l ] = δ jl . This

requirement, which leads to the normalization condition

d 3r [u i∗ (r)u j (r) − vi∗ (r)v j (r)] = δi j , (80)

where (r) is taken to be real for now. This ansatz, which is analogous to the side-

mode probe expansion familiar in nonlinear optics, will be useful in the discussion

of matter-wave mixing and squeezing of the following sections. In these cases,

2

The kinetic energy contribution is sometimes referred to as the “quantum pressure” term.

NONLINEAR OPTICS OF DE BROGLIE WAVES 19

though, it will become necessary to remove the assumption that (r) is real, i.e.,

go past pure density arguments.

The functions u j (r) and v j (r) satisfy the coupled equations

(82)

−hωv j (r) = [H0 − μ + 2g2 (r)]v j (r) + g2 (r)u j (r),

where H0 = −(h 2 /2M )∇ 2 ) + Vtrap (r). These equations must generally be solved

numerically for the trap potential at hand [34–40]. For spherical traps, the solutions

of Eqs. (82) are characterized by the quantum numbers n, l, and m, where n, is

the radial mode number, l is the angular momentum of the excitation, and m is its

z component. For axially symmetric traps, m is still a good quantum number.

B. FINITE TEMPERATURES

At finite temperatures, a nonvanishing portion of the atoms is in states other

than the condensate ground state, and one must account for this fact as well as

for so-called anomalous Bose correlations, a matter-wave analog of “squeezing”

contributions in quantum optics. We limit our review to a brief outline of some of

the general techniques used to approach this problem, without going into any detail

[41]. In addition to introducing standard approximations, this discussion paves the

way to the discussion of wave mixing of Sect. V, in particular, matter-wave phase

conjugation, which relies explicitly on the generation of anomalous correlations

in a Schrödinger field.

Our starting point is again the Heisenberg equation of motion (36) for the

Schrödinger field operator, including the s-wave two-body interaction, and the

ˆ

decomposition of (r, t) into a condensate and a noncondensate contribution; see

Eq. (63). In Sect. V we will use an expansion of the Schrödinger field on a restricted

set of matter-wave modes to handle the correlation functions of operator products

of the form ˆ †ˆˆ “exactly,” following standard quantum optics approaches.

Here, we follow a “condensed matter” approach, where the Heisenberg equations

of motion are truncated by an approximate factorization scheme. We first express

the product of the three field operators appearing in the Heisenberg equations of

motion as

ˆ †

ˆˆ = ||2 + 2||2

ˆ ′ + 2

ˆ ′† + ∗

ˆ ′

ˆ ′ + 2

ˆ ′†

ˆ +

ˆ ′†

ˆ ′

ˆ′ (83)

instead of performing the factorization ansatz (69). We then introduce the self-

consistent mean-field approximation,

ˆ ′†

ˆ ′

ˆ ′ ≃ 2

ˆ ′†

ˆ ′

ˆ ′ +

ˆ ′

ˆ ′

ˆ ′† . (84)

20 P. Meystre

The factor of 2 in this equation results from the sum of the direct (Hartree) and

exchange (Fock) contributions, which are identical in the case of a shapeless two-

body interaction.

As before, the equation of motion for the condensate wave function (r) is

obtained by taking the expectation value of the Heisenberg equation of motion

(83) to give

2 2

h ∇ ˆ † (r)(r)

ˆ (r)

ˆ

− + Vtrap (r) − μ (r) + g = 0, (85)

2M

2 2

h ∇

− + Vtrap (r) − μ (r) + g[n c (r) + 2n ′ (r)](r) + gm ′ (r)∗ (r) = 0.

2M

(86)

In this expression, we have introduced [41] the condensate density,

ˆ ′† (r)

n ′ (r) ≡ ˆ ′ (r)
, (88)

ˆ ′ (r)

m ′ (r) ≡ ˆ ′ (r)
. (89)

The equation of motion for the condensate excitations, which are described by

ˆ ′ (r, t), is readily obtained by substracting Eq. (85) from the

the field operator

Heisenberg equation of motion (83). One finds

2 2

∂ ˆ′ h ∇ ˆ ′ (r, t) + g(

ˆ †

ˆˆ −

ˆ †

ˆ
).

ˆ

ih (r, t) = − + Vtrap (r) − μ

∂t 2M

(90)

Consistent with the mean-field approximation (84), we approximate the bilinear

operator products in this expression as

ˆ † (r)(r)

ˆ ˆ † (r)(r)
,

≃ ˆ

(91)

ˆ (r)

(r) ˆ ˆ (r)
,

≃ (r) ˆ

NONLINEAR OPTICS OF DE BROGLIE WAVES 21

so that

ˆ † (r)(r)

ˆ (r)

ˆ ˆ † (r)(r)

− ˆ (r)

ˆ ˆ † (r)(r)

≃ 2 ˆ ˆ ′ (r) + (r)

ˆ (r)

ˆ ˆ ′† (r)

(92)

and

2 2

∂ ˆ′ h ∇ ˆ ′ (r, t)

i h (r, t) ≃ − + Vtrap (r) − μ

∂t 2M

ˆ ′ (r, t) + m(r)

+ g[2n(r) ˆ ′† (r, t)]. (93)

density n(r) via

ˆ † (r)(r)

n(r) ≡ ˆ ˆ ′† (r)

= |(r)|2 + ˆ ′ (r)
≡ n c (r) + n ′ (r) (94)

ˆ (r)

m(r) ≡ (r) ˆ ˆ ′ (r)

= (r)2 + ˆ ′ (r)
≡ |φ(r|2 + m ′ (r). (95)

It can be shown that Eqs. (86) and (93) can also be derived from the so-called

Hartree–Fock–Bogoliubov Hamiltonian [41, 42],

2 2

1

h ∇

HHFB = d 3r ∗ (r) − + + Vtrap (r) − μ + g |(r)|2 (r)

2M 2

2 2

+ d 3r ˆ ′† (r) − h ∇ + + Vtrap (r) − μ + 2gn(r) ˆ ′ (r)

2M

g ˆ ′† (r)

ˆ ′† (r) + H.c].

+ d 3r [m(r) (96)

2

(97)

ˆ ′† (r) = u ∗j (r)α̂ †j − v j (r)α̂ j

where the operators α̂ j satisfy Bose commutation relations. Under this transfor-

mation, the Hartree–Fock–Bogoliubov Hamiltonian (96) then takes the diagonal

22 P. Meystre

form

h2∇ 2

1

3 ∗ 2

HHFB = d r (r) − + + Vtrap (r) − μ + g|(r)| (r)

2M 2

†

− E j d 3r |v j (r|2 + E j α̂ j α̂ j , (98)

j j

where the functions u j (r) and v j (r) are given by the solutions of the coupled

Hartree–Fock–Bogoliubov eigenvalue equations

h2∇ 2

− + Vtrap (r) − μ + 2gn(r) u j (r) − gm(r)v j (r) = E j u j (r),

2M

2 2 (99)

h ∇

− + Vtrap (r) − μ + 2gn(r) v j (r) − gm ∗ (r)u j (r) = −E j v j (r).

2M

†

ˆ ′ (t, t) = u j (r)α̂ j e−i E j t − v ∗j (r)α̂ j ei E j t ,

(100)

j

into the equation of motion (93). This latter approach, which is more familiar to the

quantum optics community, leads to a simple interpretation of the quasi-particles

in terms of probe side modes of the Schrödinger field.

The preceding section showed that the departure of a Bose condensate from its

mean-field dynamics can be evaluated in a framework closely related to probe

spectroscopy and of the probe field analyses familiar from nonlinear and quantum

optics. The excitation of these side modes, or quasi-particles in the language of

manybody theory, results from the nonlinear dynamics associated with the cubic

nonlinearity of the system, that is, two-body collisions. In optics, cubic nonlinear-

ities are of course known to lead to four-wave mixing phenomena, hence it should

be obvious at this point that similar effects will also be possible with matter waves.

Four-wave mixing and the phase conjugation of atomic waves were first pro-

posed in [5, 43, 44]. The original theory, which predates the demonstration of

atomic Bose-Einstein condensation, used the near-resonant dipole–dipole inter-

action as a source of two-body collisions. In condensates, however, the interac-

tion with optical fields must typically be kept far off-resonant in order to avoid

NONLINEAR OPTICS OF DE BROGLIE WAVES 23

fore ground-state collisions. However, the mathematical form of the nonlinear

Schrödinger equation describing these two situations is identical, at least in the

shapeless approximation, so that the original predictions can be extended to the

situation of s-wave scattering without difficulty.

The first verification of matter-wave phase conjugation was realized by W. D.

Phillips and co-workers in a 23Na condensate [30] (see Fig. 1). The experimental

geometry involved atoms in one hyperfine state only, the four modes involved in

the mixing process being distinguished by their center-of-mass momentum. Mode

separation was achieved via Bragg scattering off an optical field. This experiment

constituted the first explicit experimental verification of a nonlinear atom optical

effect. Shortly thereafter, several other nonlinear atom optical effects were experi-

mentally demonstrated, including matter-wave superradiance [45], phase-coherent

matter-wave amplification [46, 47], and the generation of matter-wave solitons

[48, 49].

A full three-dimensional numerical solution of a closely related situation was

given [50], which found excellent agreement with the experimental work at

National Institute of Standards and Technology (NIST). We first review that analy-

sis, which relies on the Gross-Pitaevskii equation. The following subsection gives

an exact quantum mechanical calculation of four-wave mixing in a somewhat

different geometry.

A. MEAN-FIELD ANALYSIS

The NIST experiments proceed by first releasing a Sodium condensate centered

at r = 0 from its trap potential at time t = 0. It then evolves solely under the

influence of its mean-field energy until some time t1 . After this period of free

evolution, optical pulses are made to interact with the condensate, leading to Bragg

scattering. This produces three moving matter-wave wave packets of momenta

p1 ≃ 0, p2 , and p3 such that the momentum differences pi − p j is much larger

than the momentum spread of the initial condensate wave packet. The experimental

time it takes to create these side modes is very short compared to the time scale

over which the wave packets evolve, and can thus be taken to be instantaneous.

As a result, the three wave packets initially overlap and are copies of the initial

condensate. As they fly apart, they interact nonlinearly to produce a fourth wave

at p4 = p1 − p2 + p3 .

In these experiments, and in contrast to the situation considered in the following

section, the condensate has only a single spin component. We describe its dynamics

by the Gross–Pitaevskii equation (68),

h2 2

∂ 2

h (r, t) = − ∇ + Vtrap (r) + g|(r, t)| (r, t). (101)

∂t 2M

FIG. 1. Contour (a) and three-dimensional (b) gray-scale renditions of the experimental realization

of matter-wave four-wave mixing in a sodium Bose–Einstein condensate. (From Ref. [30]. Courtesy

S. Rolston.)

NONLINEAR OPTICS OF DE BROGLIE WAVES 25

Immediately after the application of the Bragg pulses, its wave function is

3

1/2 ipi ·r/h

(r, t1 ) = (r) fi e , (102)

i=1

where f i = Ni /N is the fraction of atoms in wave packet i, with i f i = 1, and

(r) is the ground-state wave function of the condensate just before the Bragg

pulse.

Following the formation of the initial wave packets, the wave function (102)

evolves and the wave packets with different momenta start to separate. During this

separation, the mean-field energy acts as a cubic nonlinearity and generates a wave

packet of central momentum p4 = p1 − p2 + p3 . It can easily be shown that for

this momentum, both total energy E(t) and momentum p(t) are conserved during

the wave packet evolution, where

p2

E(t) = (t)| + g|(t)|2 |(t)
(103)

2M

and

form

4

(r, t) = ϕi (r, t)ei(ki ·r−ωi t) , (105)

i=1

where ki = pi /h and

hki2

ωi = . (106)

2M

In Eq. (105) we assumed that the envelopes ϕi (r, t) are slowly varying in space

and time on the scales of ωi−1 and ki−1 .

Substituting the form (105) into the Gross–Pitaevskii equation (101), collecting

in the familiar way of nonlinear optics terms multiplying the same phase factors

26 P. Meystre

[51], eliminating rapidly varying terms and keeping only the phase-matched terms

yields the set of four coupled partial differential equations for the envelopes ϕ(r, t),

h∇ 2

∂ hki i

+ ∇ −i ϕi (r, t) = − g δ(ki + k j − km − kn )

∂t M 2M h j,m,n

(107)

where each of the indices can take any value between 1 and 4.

The momentum and energy conservation conditions implicit in the Kronecker

delta functions in these equations,

ki + k j − km − kn = 0 (108)

and

ωi + ω j − ωm − ωn = 0, (109)

these conditions corresponds to self-phase modulation and the second one to cross-

phase modulation. They are known from nonlinear optics to lead to effects such

as self-focusing and defocusing, but do not involve any real exchange of particles.

What this implies in the present context is that these contributions cannot lead

to the excitation of a new side mode from the three initial wave packets. Indeed,

particle exchange between the various wave packets can only occur when all four

indices are different, while at the same time conservation of momentum and energy

are satisfied.

The momentum conservation condition (108) implies that

ki + k j = km + kn = κ. (110)

we have then ki = −k j and km = −kn , and the four-wave mixing process takes

the form of degenerate four-wave mixing [13, 51]. That is, all momenta are equal

in magnitude. We remark at this point that it is known from quantum optics that

degenerate four-wave mixing may be interpreted in terms of real-time holography.

The analogy between optics and atom optics therefore indicates that it is possi-

ble to achieve matter-wave holography via this four-wave mixing process [52].

The quantum optics analogy also leads to a direct interpretation of matter-wave

NONLINEAR OPTICS OF DE BROGLIE WAVES 27

four-wave mixing in terms of density gratings: two of the wave packets, say those

of momenta ki and km , form a density grating from which the wave packet of

momentum k j is scattered, producing the conjugate, of momentum kn , of the mth

packet. We use a similar interpretation in Sect. VI to discuss the mixing of optical

and matter waves.

Alternatively, it is possible to think of atomic four-wave mixing in terms of a

scattering process in which one particle is annihilated in each wave packet belong-

ing to an initially populated pair, and simultaneously one particle is created in each

of two wave packets of the other pair, one of which is initially populated and the

other is initially in a vacuum. In optics terms, four-wave mixing removes one atom

each from the “pump” beams, and adds one each in the “probe” and “signal” beams.

The explicit form of the four-wave mixing equations of motion is readily ob-

tained from Eqs. (107) and read

h∇ 2

∂ hk1

+ ∇ −i ϕ1 (r, t)

∂t M 2M

ig ig

=− (|ϕ1 |2 + 2|ϕ2 |2 + 2|ϕ3 |2 + 2|ϕ4 |2 )ϕ1 − ϕ2 ϕ3∗ ϕ4 , (111)

h h

the other three equations being obtained by cyclic permutations. The first four terms

on the right-hand side are self-phase and cross-phase modulation contributions.

The factors of 2 in the cross-phase modulation contributions result from nonlinear

nonreciprocity, an effect also familiar from nonlinear optics. The last term is the

source term which either creates or annihilates particles in the wave packet being

propagated. These equations were solved numerically in [50, 53] and found to be

in excellent agreement with experiments. One typical numerical example in shown

in Fig. 2.

The preceding analysis uses a mean-field description to analyze the dynamics of

four-wave mixing in a multicomponent sodium condensate. We have seen earlier

that this approach makes strong implicit assumptions about the coherence proper-

ties of the system. While these are reasonable for large condensates, their validity

is much less clear at small particle numbers, and in particular when condensate

side modes build up from noise. This section addresses the question of the quan-

tum statistics of weakly excited side modes. Provided that only a few modes of

the system are actively involved in the dynamics, one can use as an alternative to

the standard manybody techniques an “essential states description” inspired from

quantum optics to obtain more accurate results. In general, such approaches still

28 P. Meystre

FIG. 2. (a)–(f ) Time sequence illustrating the generation of a fourth matter wave out of three initial

waves created out of a condensate by Bragg pulses. The three-dimensional gray-scale rendition at the

end of the process should be compared to Fig. 1b. These are results of theoretical simulations of the

NIST matter-wave four-wave mixing experiments. (From Refs. [50, 53]. Courtesy P. Julienne.)

Occasionally, however, there is a situation that can be handled to all orders in the

fields. The example we present in the following is such a case.

We consider a Bose–Einstein condensate of 23Na atoms in the F = 1 hyperfine

ground state, with the three internal atomic states |m F = −1 , |m F = 0 , and

NONLINEAR OPTICS OF DE BROGLIE WAVES 29

FIG. 2. (Continued )

trap. It can be shown [54, 55] that the three-component vector Schrödinger field,

ˆ −1 (r, t),

Ψ̂(r, t) = { ˆ 0 (r, t),

ˆ 1 (r, t)}, (112)

p2

H= ˆ m† (r, t)

dr + U (r) ˆ m (r, t)

m 2M

h ˆ 1

ˆ 1

ˆ 1 †

ˆ1 + †

ˆ −1

ˆ −1 †

ˆ −1

ˆ −1 ]}†

+ dr{(c0 + c2 )[

2

ˆ 0 †ˆ 1

ˆ 0 ( †

ˆ −1

ˆ1 + †

ˆ −1 )] + c0

ˆ 0

ˆ 0

ˆ 0

ˆ0 † †

+ 2

ˆ 1†

+ 2(c0 − c2 ) ˆ 1 † ˆ

ˆ −1 −1

ˆ 1†

+ 2c2 (

† ˆ ˆ

ˆ −1 0 0 + H.c)}. (113)

In the language of nonlinear optics, the three terms quartic in one of the field

ˆ i†

operators only, i.e., of the form ˆ i†

ˆ i

ˆ i , are self-defocusing terms; the terms

involving two hyperfine states conserve the populations of the individual spin states

and merely lead to phase shifts; and the terms involving the central mode ˆ 0 and

30 P. Meystre

interaction, involving, e.g., the annihilation of a pair of atoms with m F = 0 and

the creation of two atoms in the states m F = ±1, leads to phase conjugation in

quantum optics and to matter-wave phase conjugation in the present case [56].

A four-wave mixing geometry can be realized when we consider a situation

where atoms in the m F = 0 state are placed in a linear superposition of two

counterpropagating center-of-mass modes of momenta ±hko . that is,

(114)

V

(115)

V

Here a01 and a02 are the annihilation operators of the two counterpropagating

†

m F = 0 modes, with [a0i , a0 j ] = δi j , i, j = 1 or 2, a1 , a−1 are the corresponding

operators for the running modes associated with m F = ±1, and V is the confine-

ment volume of the condensate. Inserting this mode expansion into the Hamiltonian

(113) and ignoring all non-phase-matched contributions yields the four-wave

mixing Hamiltonian

h 2 k02 hc0

H= N̂ + N̂ ( N̂ − 1)

2M 2

hc2 † † † † † †

+ (a a a1 a1 + a−1 a−1 a−1 a−1 − 2a1 a1 a−1 a−1

2 1 1

† † † †

+ 2(a1 a1 + a−1 a−1 )(a01 a01 + a02 a02 )

† † † †

+ 4a1 a−1 a01 a02 + 4a1 a−1 a01 a02 , (116)

† † † †

N̂ = a1 a1 + a−1 a−1 + a01 a01 a02 a02 . (117)

ments is related to the conservation of particle number: while the photon number

is not a conserved quantity, the number of atoms is, in the absence of losses. This

leads to important conservation laws, which we use in the following to describe

the dynamics of the system exactly. The most obvious conserved quantity of the

NONLINEAR OPTICS OF DE BROGLIE WAVES 31

Hamiltonian (117) is the total number of atoms, as follows from the commutator,

[ N̂ , H] = 0 (118)

† †

D̂ 0 = a01 a01 − a02 a02 , (119)

† †

D̂ = a1 a1 − a2 a2 , (120)

are also conserved. These two conservation laws follow directly from the fact that

the Hamiltonian (116) describes the creation and annihilation of bosonic atoms in

pairs. For example, the annihilation of two atoms in the center-of-mass modes 1

and 2 of the m F = 0 hyperfine state, described by the operators pair a01 a02 , results

† †

in the creation of a pair of atoms in the m F = ±1 spin states via a1 a−1 .

Together with the conservation of the total number of atoms, these conservation

laws yield the two additional conserved quantities,

† †

N̂ 1 ≡ a1 a1 + a01 a01 (121)

and

† †

N̂ 2 ≡ a−1 a−1 + a02 a02 . (122)

bra for this four-wave mixing system analogous to the Schwinger coupled boson

representation used in [57] for the description of two-mode condensates and in

[58] for the determination of the condensate ground state. However, the present

situation requires that these considerations be extended to a compound angular

momentum representation [59, 60].

We proceed by introducing the spinor operators a1 and a2 ,

a01 a2

a1 ≡ and a2 ≡ (123)

a1 a02

⎡ † † ⎤

a01 a1 + a01 a1

† 1⎢1 † † ⎥

S1 ≡ a1 σ a1 = ⎣ (a a − a01 a1 ) ⎦ (124)

2 i †01 1 †

a01 a01 − a1 a1

32 P. Meystre

and

⎡ † † † ⎤

a2 a02 + a02 a2

† 1⎢1 † †

S2 ≡ a2 σ a2 = ⎣ (a a − a a ) ⎦ , (125)

⎥

2 i †02 2 † 02 2

a2 a2 − a02 a02

where σ is the Pauli spin operator. The Casimir operators K j ≡ S2j associated with

the angular momenta S j are also constants of motion, since

N̂ j N̂ j

Kj = +1 . (126)

2 2

S ≡ S1 + S 2 (127)

h 2 k02 hc0

H= N̂ + N̂ ( N̂ − 1)

2M M

2

N̂ D̂ 0

+ 2hc2 S 2 − − . (128)

2 2

Together with the conserved Casimir operators, this form of the four-wave mixing

Hamiltonian suggests expressing the state of the system in terms of the complete

set of quantum numbers associated with the eigenstates of the operators S21 , S22 , S2 ,

and Sz . The Hamiltonian (128) can clearly be diagonalized in terms of these states,

yielding a complete set of eigenstates and eigenenergies.

To illustrate how this works, we consider a condensate consisting of N atoms

such that initially N1 = N2 = N /2. We further assume that there are m ≪ N /2

atoms in the hyperfine state m F = 1 and none in the state m F = 0. In the “natural”

basis of the operators {K 1 , S1z , K 2 , S2z }, the initial state of this system is described

by the state vector

N N N N

|φ(0)
=

, − m; , −

. (129)

4 4 4 4

NONLINEAR OPTICS OF DE BROGLIE WAVES 33

N

N

N N

|φ(0)
= C − m, − ; S, −m

, ; S, −m ,

(130)

S

4 4 4 4

where

N N

N N

C(S1z , S2z ; S, −m) ≡ , ; S, −m

4 4 4 4

are Clebsch–Gordan coefficients [61], which are nonzero only for Sz = S1z +

S2z = −m.

This conservation of Sz under the Hamiltonian (128) further implies that the

state vector of the system is given at time t by

N N

|φ(t)
= α S (t)

, ; S, −m

S

4 4

≡ α S (t)|S, −m
, (132)

S

where we have in the second equality made explicit use of the value of the con-

served quantities K 1 , K 2 , and Sz to simplify the notation via

N N

, ; S, −m → |S, −m
. (133)

4 4

Note that this simplification is not general, but is appropriate for the initial condition

at hand.

The equations of motion for the probability amplitudes α S (t) follow from the

Schrödinger equation. For a condensate containing N atoms they read, in a frame

rotating at the frequency hk02 N /2M + c0 N (N − 1)/2,

N N

α S (t = 0) = C − m, − ; S, −m .

4 4

We can apply these results to the study of the dynamics of population exchange

between the different modes of the condensate. For instance, the population of the

34 P. Meystre

m F = 1 hyperfine spin state can readily be determined from the expectation value

of S1z . With Eqs. (122) and the definition of S1z , we find

† N

a1 a1
= − S1z
. (135)

4

2

S1z
= p

α S (t)C( p, −( p + m); S, −m

, (136)

p

S

N

N N N

Î =

4 , p1 ; 4 , p2 4 , p1 ; 4 p2

(137)

p1, p2

and used the simplified notation (133) as well as the property that the Clebsch–

Gordan coefficients’ are nonzero only for Sz = S1z + S2z . Equation (136) can be

evaluated numerically.

The evolution of the population of the m F = 1 side mode is shown in Fig. 3

for N = 100 atoms in the system. Case (a) illustrates the buildup from noise,

†

m = 0, while in case (b) the initial mode population is a1 a1
= m = 5. In both

cases, the side-mode population exhibits an initial growth to the point where it

contains about one-third of the atoms in the first case and about half of the atoms

in the second. This is followed by a collapse to a quasi-steady-state population,

as well as a subsequent revival at 2c2 t1 = π. This dynamics then repeats itself

periodically, with revivals at at 2c2 tn = π n, independently of N.

FIG. 3. Evolution of the population of the m F = 1 side mode for N = 100 atoms in the system.

Case (a) illustrates the buildup from noise, m = 0, while in case (b) the initial mode population is

m = 5. (From Ref. 56.)

NONLINEAR OPTICS OF DE BROGLIE WAVES 35

in two-photon Jaynes–Cummings [62]. During the periods of collapse, one has

S j z = −m/2, so that all modes are almost equally macroscopically populated

† † †

with a01 a01 = N /4 − m/2, a1 a1 = N /4 + m/2, a02 a02 = N /4 + m/2 and

†

a2 a2 = N /4 − m/2.

A particularly interesting prediction of this analysis is the possibility to obtain

quantum correlations between side modes. In optics, four-wave mixing provides a

method to study purely quantum mechanical effects such as squeezing and nonclas-

sical states of the radiation field, and also to prepare states of composite systems

exhibiting strong quantum mechanical entanglement [63]. These states are of im-

portance in tests of the foundations of physics as well as quantum information

processing such as quantum cryptography [64, 65] and quantum computing [66].

Macroscopic quantum states of massive particles present an interesting alterna-

tive to all-optical systems, hence it is worthwhile to determine to what extent

quantum entanglement between side modes can be achieved in Bose–Einstein

condensation.

One can quantify the amount of quantum entanglement between conden-

sate modes by determining the extent to which the Cauchy–Schwarz inequal-

ity is violated by the second-order cross-correlations functions between modes

[63]. In particular, for “classically looking” optical system with positive Glauber

P representations, the single-time two-mode second-order cross-correlation func-

tion is bound by the “classical” upper bound

G i, j (t) ≤ G i (t)G j (t) . (138)

In case the P representation is not positive or does not exist, in contrast, the upper

bound is higher, namely,

G i, j (t) ≤ G i (t) + G i (t) G j (t) + G i (t) . (139)

order correlation functions

(1) †

G j (t) ≡ φ(t)|a j a j |φ(t)
(140)

(2) † †

G i j (t) ≡ φ(t)|ai ai a j a j |φ(t)
(141)

36 P. Meystre

(2) † †

G j (t) ≡ φ(t)|a j a j a j a j |φ(t)
. (142)

modes m F = ±1 can be expressed in terms of the z component of the individ-

ual pseudo-spins as

(2) N N

G −1,1 (t) = − S1z − S2z

4 4

2

N N

= − (S1z + S2z ) + S1z S2z , (143)

4 4

where

2

[N /2]

S1z S2z
= p(− p − m)

αs (t)C( p, −( p + m); S, m

(144)

p

s=m

Figure 4 compares the time dependence of the normalized central-mode–side-

mode correlation function

(2)

(2) G 01,1 (t)

R01,1 (t) ≡ (145)

(2) (2)

G 01 (t)G 1 (t)

FIG. 4. Time evolution of the one-time normalized central mode-side mode correlation function

(2) (2)

R01.1 (t) (lower curve) and of the normalized side-mode–side-mode correlation function R−1.1 (t)

(upper curve) for N = 100 and (a) m = 0, (b) m = 5. The shaded region is classically forbidden.

(From Ref. 56.)

NONLINEAR OPTICS OF DE BROGLIE WAVES 37

(2)

(2) G −1,1 (t)

R−1,1 (t) ≡ (146)

(2) (2)

G 1 (t)G −1 (t)

for (a) the case m = 0 where the side mode builds up from quantum fluctuations

and (b) the case m = 5 of an injected signal.

These results illustrate how the correlations between the central mode and side

modes do satisfy the classical Cauchy–Schwarz inequality, while the side-mode–

side-mode cross-correlations violate them. The violation is particularly strong in

the case of buildup from noise, as should be intuitively expected. In that case the

hyperfine sidemodes m F = ±1 play symmetric roles, thus,

(2) (2) (1)

G −1,1 (t) = G 1 (t) + G 1 (t), (147)

(2)

i.e., R−1,1 = 1 Equation (139) then becomes an equality, leading to the maxi-

mum violation of the classical Cauchy-Schwarz inequality allowed by quantum

mechanics.

The difference in the behavior of the two-mode correlation functions between

side modes and those involving one central and one side mode can be intuitively

† †

understood from the form of the wave-mixing term a1 a−1 a01 a02 appearing in

the Hamiltonian (116). Indeed, the coupling between side modes, involving two

† †

annihilation operators, is reminiscent of the interaction a1 a2 in the Hamiltonian of

parametric amplification leading to squeezing and quantum entanglement between

two side modes. In contrast, the coupling between central and side modes involves

both an annihilation and a creation operator.

From these results, it appears that multicomponent condensates offer a fascinat-

ing potential method to create quantum entanglement at a truly macroscopic level,

a possibility made even more attractive by the fact that these systems suffer little

from dissipation, since they consist of ground-state atoms. The final section extends

these results to the nonlinear mixing of optical and matter wave fields, opening up

the additional possibility of optically controlling the quantum statistical properties

of Schrödinger fields.

We have mentioned that conventional nonlinear optics relies for its description

on the elimination of the material dynamics, while in nonlinear atom optics one

eliminates (part of) the electromagnetic field, resulting in effective atom–atom

interactions. One should keep in mind, however, that these represent limiting cases.

38 P. Meystre

Outside these two regimes the atomic and optical fields are dynamically coupled,

and neither field is readily eliminated. This leads to intriguing new possibilities,

including the nonlinear mixing of optical and matter waves that we investigate in

this last section.

We first discuss the parametric amplification of matter waves resulting from the

coupling between a Bose–Einstein condensate and both a strong laser field and a

weak single mode of a ring cavity. The strong pump laser is treated as a classical,

undepleted light field. It is assumed to be detuned far enough away from resonance

that spontaneous emission may be safely neglected. The cavity field, or ”probe”

field, is assumed to be weak relative to the pump, and is treated fully quantum

mechanically as a dynamical variable.

Assuming that the probe field begins in or near the vacuum state, and the atomic

field consists initially of a trapped condensate, the initial dynamics is dominated by

a single process: the absorption of a pump photon by a condensate atom followed

by the emission of a probe photon. This is a two-photon virtual transition in which

the excited atomic state population remains negligible. Due to atomic recoil, the

absorption/emission process transfers the atom from the condensate ground state

to a new state that is shifted in momentum space by the two-photon recoil. This

new state, which is a momentum side mode of the original condensate, can be

thought of as a second condensate component. It may or may not be in the same

internal ground state as the original condensate, depending on the polarizations of

the pump and probe photons. If the initial and final magnetic sublevels are different,

as might be the case in a spinor condensate, the transition would be termed a Raman

transition. This is to be contrasted with the case of a scalar condensate, in which

the initial and final sublevels are identical and the light-atom interaction may be

thought of as Rayleigh scattering or as two-photon Bragg scattering. The model

discussed in this section deals specifically with this Bragg-Rayleigh scheme, but

it can be extended to the Raman problem with only minor modifications.

The physics underlying the parametric amplification of optical and matter waves

can be understood intuitively in essentially classical terms: as the matter-wave side

mode is populated, it begins to interfere with the original condensate, resulting in

fringes [67]. These fringes are seen by the pump and probe fields as a spatial density

grating, which then enhances the photon scattering process. This interplay between

interference fringes and scattering can act as a positive feedback mechanism,

in which case the system is unstable and characterized by exponential growth.

Any small signal, including quantum noise, is sufficient to trigger the instability,

resulting in the generation of exponentially growing side-mode and probe fields.

Of course, this exponential growth is eventually reversed by high-intensity effects,

so that the long-time dynamics are characterized by large-amplitude nonlinear

NONLINEAR OPTICS OF DE BROGLIE WAVES 39

oscillations. In many ways, this system is an extension into the ultracold regime

of the so-called collective atomic recoil laser (CARL) [68–70] We concentrate

here on the small-signal regime, characterized by exponentially growing fields.

As we shall see, one particularly interesting property of this system is that the

quantum state of the probe and side-mode fields depends strongly on the initial

conditions, so that, e.g., by injecting a small coherent light field into the probe,

one can create an entirely different quantum state than that generated from the

amplification of quantum vacuum fluctuations. The differences are manifested in

the quantum statistics of the individual field modes, as well as in nonclassical

correlations and entanglement between them.

Under conditions of far off-resonant excitation, the effective Hamiltonian

describing this system is [71]

h2q 2 †

†

H = d 3q ĉ (q)ĉ(q) + hδk b̂kλ b̂kλ

2M kλ

∗

g g ′ ′

kλ †

+ d 3 qh kλ b̂kλ b̂k′ λ′ ĉ† (q)ĉ(q + k − k′ ), (148)

′

kλk λ ′ δ

hq, b̂kλ annihilates a photon of momentum hk and polarization λ, δ is the detuning

between the laser–atom frequency detuning, and gkλ is the atom-field coupling

constant. This Hamiltonian yields the Heisenberg equations of motion,

d hq 2 g ∗ gk′ λ′ †

kλ

ĉg (q) = −i ĉg (q) − i b̂kλ b̂k′ λ′ ĉg (q + k − k′ ) (149)

dt 2M kλk′ λ′

δ

and

∗

d gkλ gk′ λ′ †

b̂kλ = −iδk b̂kλ − i d 3q ĉg (q)b̂k′ λ′ ĉg (q + k − k′ ), (150)

dt k′ λ′

where δk = c|k| − δ.

The nonlinearity in the effective Hamiltonian (148) allows for cross-phase mod-

ulation and four-wave mixing phenomena between the atomic and optical fields.

The phase shift which the optical field acquires due to cross-phase modulation

with the atomic field is

|gkλ |2 N̂

φopt = t, (151)

δ

where N̂ is the operator for the total number of atoms, which may or may not be

40 P. Meystre

is fixed, this nonlinear phase shift is nothing more than the dispersive shift to the

index of refraction found in linear optics. Nontrivial effects may occur in open

systems, e.g., if the number of atoms fluctuates in response to changes in the

optical field, but otherwise leads only to a negligible shift in the optical dispersion

relation. Similarly, the phase shift acquired by the atomic field due to cross-phase

modulation,

kλ

φat = t, (152)

kλ

δ

is simply the spatially independent part of the Stark shift, which has no dynamical

effect on the atomic density.

In the examples we consider in the following, the Stark shift and the dispersion

of the optical field may be safely neglected. We focus instead on the effects of

four-wave mixing between atomic and optical fields, which leads to parametric

amplification and the generation of entanglement between atomic and optical fields.

In order to extract the basic physics underlying the four-wave mixing of optical

and matter waves, we ignore cavity losses and treat the pump laser field classically

in the following. The effective Hamiltonian (148) then reduces to

q2

H = hωrec b̂† b̂ + d 3 q 2 ĉ† (q)ĉ(q) + χ [ĉ† (q)ĉ(q − K)b̂ + H.c.] ,

K

(153)

where b̂ is the photon annihilation operator for the probe mode, whose frequency

is detuned from that of the pump by hωrec , and

K = k L − k. (154)

g

χ= , (155)

2|δ|ωrec

where g is short hand for the coupling constant gkλ of the probe mode and is

the pump Rabi frequency.

We consider specifically the case where the atomic field initially consists of a

condensate well below the critical temperature Tc . Assuming that its initial mo-

mentum width is small compared to the recoil momentum hK, it is reasonable to

approximate it as a plane wave at q = 0. The effect of the optical fields is then to

NONLINEAR OPTICS OF DE BROGLIE WAVES 41

by integer multiples of hK. Making use for expediency of the symmetry breaking

approach of Sect. IV, we replace the condensate field operator ĉ(0) by a c-number

plus a perturbation,

√

ĉ(0) = N + ĉ0 , (156)

Bogoliubov approach, except that instead of computing a quasi-particle spectrum,

we proceed along the lines of the linear stability analyses familiar from quantum

optics. Specifically, we derive time-dependent equations

√ of motion for the per-

turbations ĉ0 about the condensate wave function N . For times short enough

that the fraction of atoms transferred into the side modes remains negligible, the

Hamiltonian (153) can be linearized, leading to

† †

√ †

Ĥ lin = hωrec [ĉ− ĉ− + ĉ+ ĉ+ + δ b̂† b̂ + χ N (b̂† ĉ− + b̂† ĉ+ + H.c.)], (157)

where ĉ± = ĉ(±K). This Hamiltonian yields a 3 × 3 set of linear equations for the

three coupled field modes (two matter waves and one optical mode),

⎛ ⎞ ⎛ √ √ ⎞⎛ ⎞

b̂ −δ

√ −χ N −χ N b̂

d ⎝ †⎠ † ⎠

ĉ− = i ⎝ χ √N 1 0 ⎠ ⎝ ĉ− , (158)

dτ

ĉ+ −χ N 0 −1 ĉ+

where τ = ωrec t. The time dependence of the three field modes is determined by

the eigenvalues of the 3 × 3 matrix on the r.h.s. of (158). These are found by solving

the characteristic equation

ω3 + ω2 − ω − + 2χ 2 N = 0, (159)

(3 + 2 )3/2 − 3 + 9

χ2N > . (160)

27

When the condition (160) is satisfied, the system is unstable and the three fields

initially exhibit exponential growth. This growth will of course be arrested by

saturation effects as soon as the side-mode populations become significant.

†

The presence of the b̂† ĉ− term in Eq. (157) describes the creation of correlated

atom–photon pairs, and is analogous to the term found in the optical parametric

amplifier [63] which describes the generation of correlated photon pairs. One of

42 P. Meystre

the most interesting applications of the optical parametric amplifier is the gener-

ation of entangled quantum optical states. A similar entanglement occurs in the

present system, except that it is now between atomic and optical field modes. A

useful measure of quantum entanglement is the second-order equal-time intensity

correlation function, defined as

(2) N̂ i N̂ j
− δi j N̂ i

gi j = . (161)

N̂ i
N̂ j

surement of the intensity difference between two modes, described by the operator

N̂ i j = N̂ i − N̂ j , (162)

(2)

(Ni j )2 = (Ni )2 − 2Ni N j gi j − 1 + (N j )2 .

(163)

(2)

For uncorrelated fields, gi j = 1, and we have the usual rule for the addition of

uncorrelated noise sources,

If, however, there are correlations between the fluctuations in the intensities of the

(2)

two modes, then we have gi j > 1, and the variance Ni j will be less than that

given by (164).

For classical fields (positive P function), the two-mode (i = j) correlations are

constrained by the Cauchy–Schwarz inequality,

gi j ≤ gii gjj . (165)

Quantum mechanical fields, however, can violate this inequality and are instead

constrained by

1/2 1/2

(2) (2) 1 (2) 1

gi j ≤ gi j + gjj + , (166)

N̂ i
N̂ j

which reduces to the classical result in the limit of large intensities. When triggered

from the vacuum, it is readily found that the single-mode correlation functions are

those of thermal fields g (2) (τ ) = 2. In this case the cross-correlation functions are

NONLINEAR OPTICS OF DE BROGLIE WAVES 43

found to be [71]

1/2

1 1/2

(2) (2) 1

g12 = g23 = 2 + 2+ , (167)

N1 + N3 N2

and

(2)

g13 = 2, (168)

where 1 corresponds to the probe mode, 2 to the −K side mode, and 3 to the +K

mode. As N1 ≫ N3 we see that the intensity correlations between the probe and

−K side mode are very close to the maximum allowed by quantum mechanics,

whereas the other two-mode correlations are considerably more classical.

B. MATTER-WAVE SUPERRADIANCE

So far, we used an optical cavity to select the probe optical field mode. Recent

experiments by W. Ketterle and co-workers, however, have demonstrated that under

appropriate conditions mode selectivity can be achieved without the use of cavities

[45]. They observed highly directional scattering of pump photons along the long

axis of a cigar-shaped condensate when the pump polarization and wave vector

were both perpendicular to the condensate axis; see Fig. 5. The optical mode is

therefore selected by the condensate geometry, and this results in the buildup of

population in a condensate side mode with a single well-defined momentum.

Typical condensates are sufficiently localized in space that scattered photons

immediately exit the condensate, with a negligible cross section for multiple scat-

tering. Due to photon recoil, however, each such scattering event transfers an atom

from the condensate state into a state which is shifted in momentum space by the

two-photon recoil momentum, as discussed in the preceding section. The positive

feedback which leads to instability and parametric gain is then provided solely by

the recoiling atoms, which, due to their slow velocity, remain in the condensate

volume long enough to influence the direction of subsequent photon scattering.

To see quantitatively how this work, it is necessary to consider in more detail

the coupling coefficients gk,λ of the Hamiltonian (148). Their explicit form is

| 0 | c|k|d 2

g(k) = |k̂ × x̂|, (169)

2|| 2hǫ0 (2π)3

where d is the magnitude of the atomic dipole moment for the transition involved.

Because the geometry of the condensate is essential in understanding matter-

wave superradiance, it is no longer sufficient to consider a free-space description.

44 P. Meystre

resonant laser beam perpendicular to the long axis. (b)–(g) show absorption images after a 20-ms time

of flight of the atoms away from the trap, for various polarizations and durations of exposure to the

incident beam. For a polarization parallel to the long axis of the condensate, (b)–(d), normal Bragg

scattering is observed. For a polarization perpendicular to the long axis, the excitation of well-defined

condensate side modes is apparent. The pulse durations for (e)–(g) are 35, 75, and 100 μs, respectively.

(From Ref. [45].)

Instead, the atomic field is now taken to be a number state in which N atoms occupy

the ground state ϕ0 (r) of the trap containing the condensate. The effect of atomic

recoil during Bragg (or Rayleigh) scattering between the pump and the vacuum

mode k is therefore to transfer atoms into the state ϕ0 (r) exp[i(k L − k)r]. This

suggests expanding the atomic field operator onto quasi-modes according to

ˆ

(r, t) = r|q
e−i(ωq +μ)t ĉq (t), (170)

q

where r|q
= ϕ0 (r) exp(iq · r), and ωq = h|q|2 /2M. This is similar to the slowly

varying envelope approximation of optical physics, the envelope being given here

by ϕ0 (r).

A discrete quantization of the q values follows from the requirement that the

operators {ĉq } obey approximately the boson commutation relations

†

[ĉq , ĉq′ ] = q|q′
≈ δq,q′ . (171)

NONLINEAR OPTICS OF DE BROGLIE WAVES 45

Due to the finite size of the ground-state wave function ϕ0 (r), this means that q

and q′ must be well separated in k-space. Hence, the summation in Eq. (170) is

taken to include the condensate mode q = 0 as well as a grid of q values as closely

spaced as is consistent with orthogonality. Clearly, this expansion is not rigorously

orthogonal and complete, but it is sufficient to account for the quantum statistical

effects which occur above the critical phase-space density.

The quasi-mode populations experience losses as the recoiling atoms eventually

propagate out of the condensate volume. The lifetime of the quasi-mode q, however,

is on the order of Tq ≡ m L q /h|q|, where L q is the length of the condensate along

q. These losses tend to destroy the coherence between condensate and quasi-mode,

which accounts for the observation of a threshold for superradiance in the MIT

experiment: for insufficient laser power, the growth of matter-wave coherence

cannot overcome the losses. As this threshold is very small, we consider only the

situation far above threshold, in which case the losses may be neglected.

An important aspect of BEC superradiance is the generation of families of

higher-order side modes due to the scattering of pump photons by the first-order

side modes, as clearly evident in Fig. 5. For the present discussion, however, we

consider a simplified model containing only the primary Rayleigh scattering pro-

cess, whereby a condensate atom is transferred to a first-order side mode by scat-

tering a pump photon of momentum k L and frequency ω L . With this simplification,

the effective Hamiltonian (148) becomes for the trap situation under consideration:

t

3 †

d 3 k hg(k)ρq (k)eiωq ĉq† b̂† (k)ĉ0 + H.c. ,

Ĥ = d khω(k)b̂ (k)b̂(k) +

q=0

(172)

where

ρq (k) = d 3 r|ϕ0 (r)|2 exp [−i(k − k L + q) · r] (173)

k L − q.

From the Hamiltonian (172), it is straightforward to derive the equation of

motion for b̂(k), which upon formal integration yields

b̂(k, t) = b̂(k, 0)e−iω(k)t − i g(k)ρq (k)eiωqt

q=0

t

× dτ e−i[ω(k)+ωq ]τ ĉq† (t − τ )ĉ0 (t − τ ), (174)

0

where the first term gives the free electromagnetic field, i.e., vacuum fluctuations,

46 P. Meystre

and the second term is the radiation field due to Rayleigh scattering. A nonzero

†

expectation value of the coherence operator ĉq ĉ0 indicates the presence of in-

terference fringes, hence the radiated field increases as fringes build up. This is

the term that leads to the instability, where the memory of previous scattering

events, stored in the matter-wave interference fringes, enhances the present rate of

Rayleigh scattering.

Equation (174) is then substituted into the equation of motion for ĉq , which in

the Markov approximation yields

d Gq †

ĉq = −i d 3 kg(k)ρq (k)b̂† (k, 0)ei[ω(k)+ωq ]t ĉ0 + ĉ ĉq , (175)

dt 2 0

where

d 3 k|g(k)|2 |ρq (k)|2 δ ω(k) + ωq

G q = 2π (176)

is the single-atom gain. In deriving Eq. (175) we have used the orthogonality of the

states {|q
} to make the approximation ρq∗ (k)ρq′ (k) ≈ |ρq (k)|2 δq,q′ , and neglected

the principal part which accompanies the δ function. If included, it would contribute

additional ground-state collisions due to the dipole–dipole interaction.

For a closed atomic system, the total number of atoms is conserved, hence

†

ĉ0 ĉ0 = N − ĉq† ĉq . (177)

q=0

†

For very short times we can therefore take ĉ0 ĉ0 ≈ N . In this case Eq. (175)

reduces to

d Gq

ĉq = N ĉq + fˆ†q (t), (178)

dt 2

where fˆq (t) is a noise operator whose correlation functions are given in the Markov

approximation by

†

fˆq (t) fˆq (t ′ )
= 0,

(179)

†

fˆq (t) fˆq (t ′ )
= G q N δ(t − t ′ ).

and hence describe the “spontaneous” scattering which occurs in the absence of

any side-mode population.

NONLINEAR OPTICS OF DE BROGLIE WAVES 47

t

ĉq (t) = e(G q /2)N t ĉq (0) + dτ e(G q /2)N τ fˆ†q (t − τ ). (180)

o

From Eq. (180) it is possible to compute the probability Pq (n, t) of having n atoms

in mode q at time t, assuming zero population at t = 0. To accomplish this we first

compute the antinormally ordered characteristic function,

yielding

2

χq (η) = e−|η| [n̄ q (t)+1] , (182)

where

corresponding to a chaotic field [63]. The number distribution for a chaotic field

is given by

1 −(n+1)

1

Pq (n, t) = 1+ , (184)

n̄ q (t) n̄ q (t)

To conclude the analysis, we still need to determine the geometric dependence

of the single-atom gain given by Eq. (176), and show that it is largest for radiation

along the long axis of the condensate. This is what allows the system to operate

without the benefit of an optical cavity, as already mentioned. We first note that

G q depends on g(k), which contains the dipole radiation pattern, as well as on

ρq (k) which depends on the geometry of the initial condensate. For a cigar-shaped

condensate, aligned along the ẑ axis, ρq (k) is a disk which lies parallel to the x̂–ŷ

plane in k-space. The dimensions of the disk in k-space are roughly the inverse of

the condensate dimensions in r-space. Thus, for a condensate whose dimensions

are large compared to an optical wavelength, the dimensions of ρq (k) are small

compared to k0 .

Since g(k) is slowly varying compared to ρq (k), it can be removed from the

integral in Eq. (176), and evaluated at the center of ρq (k). In addition, we neglect

the recoil shift ωq in the δ function, as it has negligible effect on the value of G q .

48 P. Meystre

The remaining integral then defines the solid angle q for the scattered radiation

associated with the qth mode according to

1

q = 2 d 3 k|ρq (k)|2 δ(|k| − k0 ). (185)

k0

This shows that only q values for which the center of ρq (k) lies at a distance k0

from the origin experience gain, a consequence of energy conservation. Thus, for

every active quasi-mode q there is a corresponding radiation direction k̂, such that

q = k0 (ŷ − k̂).

We can obtain a good estimate for q by taking |ρq (k)|2 to be an ellipsoid solid

with the inverse dimensions of the condensate. This gives

2 −1/2

4π 2 L 2

q = 2 2 cos θk̂,ẑ + sin θk̂,ẑ , (186)

k0 W W

where L is the length of the condensate along the ẑ axis, W is the radial diameter,

and θk̂,ẑ is the angle between the radiation direction and the long axis of the

condensate. Thus q is maximized for radiation along ẑ and −ẑ where it is given

by q = 4π/k02 W 2 . It is important to note that for the isotropic case L = W there

is no preferred direction, and a ring of radiation is instead observed.

Taking into account all of these considerations, the expression for the single-

atom gain becomes

sin2 θk̂,x̂

Gq = G , (187)

cos2 θk̂,ẑ + (L/W )2 sin2 θk̂,ẑ

where

3| |2 Ŵ

G= (188)

8||2 k02 W 2

is the maximum single-atom gain, Ŵ = k03 d 2 /3π hǫ0 being the single-atom spon-

taneous decay rate, and θk̂,x̂ is the angle between the radiation and polarization

directions. For the parameters of the MIT experiment we find G ≈ 4 × 10−4 · I,

where I is the laser intensity in mW/cm2, and G is given in hertz. A rough estimate

of the duration of a superradiant pulse for the case N = 106 and I = 100 mW/cm2

is t = ln(N )/G N ≈ 150μs, in excellent agreement with experimentally observed

time scales.

When modes with different values of G q compete, the competition is “unfair”

and the mode with the largest G q generally depletes all of the condensate atoms

before the populations of the other modes have a chance to grow. Modes with the

NONLINEAR OPTICS OF DE BROGLIE WAVES 49

same G q , such as the quasi-modes corresponding to radiation along the ẑ and −ẑ

directions, instead compete “fairly,” and while the interplay is highly sensitive to

the random initial conditions, neither mode necessarily wins, i.e., there is no real

“winner-takes-all” effect, and often a “tie” will occur.

Phase-coherent amplification goes one step further than the superradiance experi-

ment just discussed: in addition to increasing the number of atoms in a given mode

of the Schrödinger field, it also preserves the phase of the state being amplified.

The idea of phase-coherent matter-wave amplification is of course implicit in the

discussion of Sect. VI. B, but while these original theoretical proposals used optical

cavities to select the required optical field modes, the superradiance experiments

show that this is actually not necessary. It is this observation which is at the heart

of the phase-sensitive amplifier recently demonstrated.

In the absence of a seed signal, the parametric amplification of the side

mode builds up from density fluctuations, the atom-optical version of “vacuum

fluctuations.” To demonstrate the phase-preserving nature of the amplification,

it it necessary to amplify an injected signal of known properties. This was re-

cently achieved in experiments by Kozuma et al. [47] and by Inouye et al. [46].

In these experiments, the seed beam was generated by exposing the condensate

to a pulsed optical standing wave that transferred atoms into the appropriate side

mode by Bragg scattering. The phase of the amplified signal was then determined

FIG. 6. Phase coherent matter-wave amplifier A weak matter wave is split off a condensate by

application of a Bragg pulse. The probe is amplified by passing through the condensate “pumped” by a

strong laser beam. The coherence of the amplified matter wave is verified by observing its interference

with a reference matter wave produced by applying a second Bragg pulse to the condensate. (From

Ref. [46].)

50 P. Meystre

FIG. 7. Input–output characteristic of the matter-wave amplifier, showing the amplification of the

probe pulse and the depletion of the condensate used as an amplifying medium. (From Ref. [46].)

by atom interferometry, using as a reference a second matter wave also split off

the condensate by Bragg scattering; see Figs. 6 and 7.

Phase-coherent matter wave amplification can be seen as both the culmination

and the “coming of age” of atom optics. Particularly when used in combination

with atom lasers, coherent matter-wave amplifiers provide an exciting new tool in

the arsenal of atom optics, with potential applications in precision measurements,

the amplification of small signals, and atom lithography. In addition, very much

as optical parametric amplifiers are central to many aspects of modern quantum

optics, including in particular the generation of squeezed light and of quantum

entanglement in optical fields, it can be expected that similar developments will

now occur in atom optics.

VII. Acknowledgments

most notably E. V. Goldstein, G. Lenz, M. G. Moore, H. Pu, O. Zobay, and E. M.

Wright. This work is supported in part by the U.S. Office of Naval Research

under Contract 14-91-J1205, by the National Science Foundation under Grant

PHY98-01099, by the U.S. Army Research Office, and by the Joint Services Optics

Program.

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ADVANCES IN ATOMIC, MOLECULAR, AND OPTICAL PHYSICS, VOL. 47

FORMATION OF ULTRACOLD

MOLECULES (T ≤ 200 μK ) VIA

PHOTOASSOCIATION IN A GAS

OF LASER-COOLED ATOMS

FRANÇOISE MASNOU-SEEUWS and PIERRE PILLET

Laboratoire Aimé Cotton, Bât. 505, Campus d’Orsay, 91405 Orsay Cedex, France

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54

II. Physical Concepts in Photoassociation and Formation of Molecules. . . . . . 57

A. Long-Range Alkali Dimer Molecules: A Pair of Atoms . . . . . . . . . . . 59

B. The Le Roy–Bernstein Law for Bound Levels: Analogy with Rydberg

Law, Scaling Laws . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64

C. Theoretical Predictions for the Photoassociation Rates . . . . . . . . . . . . 70

D. The Reflection Principle for Calculation of Franck–Condon Factors . . . 73

E. The Nodal Structure of the Zero-Energy Scattering Wavefunction. . . . . 75

F. A Simple Theory of Photoassociation . . . . . . . . . . . . . . . . . . . . . . 77

G. How to Make a Molecule in the Ground State or Lower Triplet State . . . 78

III. Ultracold Molecule Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80

A. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80

B. Experimental Setup in the Orsay Experiment . . . . . . . . . . . . . . . . . . 80

1. Cold Atomic Source . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80

2. Photoassociation Laser . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

3. Detection of the Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . 84

C. Photoassociation Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84

1. Trap-Loss Spectrum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85

2. Ion Spectrum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88

D. Mechanism for Cold Molecule Formation . . . . . . . . . . . . . . . . . . . . 91

E. Translational Temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93

F. Photoassociation Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94

G. Rotational and Vibrational Temperatures . . . . . . . . . . . . . . . . . . . . 96

H. Other Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99

IV. Theoretical Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100

A. Dynamics: Determination of Vibrational Wavefunctions for

Photoassociated Molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101

1. Mapped Fourier Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101

2. Numerov Approach and Other Methods . . . . . . . . . . . . . . . . . . . 107

3. Analytical Treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108

B. The Urgent Need for Accurate Molecular Potential Curves and

Electronic Dipole Transition Moments . . . . . . . . . . . . . . . . . . . . . . 108

V. Present Status of the Comparison between Experiment and Theory:

Formation Rates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109

All rights of reproduction in any form reserved.

ISBN 0-12-003847-1/ISSN 1049-250X/01 $35.00

54 F. Masnou-Seeuws and P. Pillet

B. Cold-Molecule Formation Rate . . . . . . . . . . . . . . . . . . . . . . . . . . 111

C. Tunneling Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114

VI. New Schemes for Making Ultracold Molecules. . . . . . . . . . . . . . . . . . . 116

VII. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117

VIII. Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120

IX. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120

I. Introduction

Interest in making cold (T < 1 K) and ultracold (T well below 1 mK) molecules

has long been recognized; among the possible applications, we may cite ultrahigh-

resolution spectroscopy measurements and metrology. Other applications can

be considered, for instance the search for an elementary dipole moment in a

paramagnetic molecule as a test of time-reversal symmetry (Kozlov and Ezhov,

1994; Hinds and Sangster, 1992; Sauer et al., 1994). Threshold laws for molecular

collisions at very low energies could also be investigated (Gray and Rice, 1985;

Forrey et al., 1989). More recently, the creation of a Bose–Einstein condensate of

molecules has appeared as a new challenge (Timmermans et al., 1999a,b, Wynar

et al., 2000, Koŝtrun et al., 2000) while Julienne et al. (1998) have proposed

creating a “molecular laser.”

In 2000, an extensive review written by Bahns et al. on the formation of cold

(T ≤ 1 K) molecules gave a detailed description of possible applications to high-

resolution spectroscopy, manipulation of molecules, cold collisions, production

of cold trimers and larger clusters, and finally Bose–Einstein condensation. Non-

optical cooling techniques were reviewed, including free-jet expansion and he-

lium buffer gas cooling, leading to subkelvin temperatures. To reach the ultracold

domain, i.e., submillikelvin temperatures, optical cooling techniques need to be

considered. However, direct laser cooling of molecules does not seem a promising

technique, and it appears more efficient first to cool the atoms and then make a

molecule out of cold atoms.

Indeed, laser cooling and trapping of atoms is now a well-mastered technique,

used in many applications such as atomic clocks. Temperatures below 10−6 K are

“easily” reached. Among the very few attempts to generalize optical cooling to

molecules, one may cite the deflection of a molecular beam achieved by Herman

et al. in 1979, and the demonstration, by Djeu and Whitney (1981), of laser cooling

by continuous anti-Stokes scattering, introduced long ago by Kastler (1950) as

“luminorefrigeration.” As discussed by Bahns et al. (1996), the main obstacle in

this research direction is that a molecule is essentially a multilevel system whereas

direct optical cooling requires a closed two-level system to recycle population.

Cooling of an atom takes place via a large number of optical pumping cycles in

which absorption and spontaneous emission transfer population from a lower level

to an upper one and back, as indicated in Fig. 1 for the case of Cs(6s) → Cs(6p3/2)

FORMATION OF ULTRACOLD MOLECULES 55

FIG. 1. (Left) Optical pumping scheme for cooling an atomic cesium sample, using the 6s →

6 p3/2 D2 resonance line. In order to cool the atom, many cycles of absorption–spontaneous emission

must be performed between the set of two (6s, f = 4) and (6p3/2, f = 5) hyperfine sublevels, varying

the red detuning of the laser. As the spontaneous emission may also be populating the (6s, f = 3) sub-

level, a repumping laser is used to put the atoms back in the upper state. (Right) The difficulty of

generalizing a direct cooling scheme to a molecule comes from the very large number of levels.

is a nuisance, as absorption can populate another level, causing population loss by

spontaneous emission to the wrong lower level. When the number of neighboring

levels is limited, as in the chosen example, this inconvenience is corrected for by use

of repumping lasers. However, the number of repumping lasers has to stay within

reasonable limits, so the procedure cannot be easily generalized to a multilevel

system such as a molecule (Bahns et al., 1996, 2000).

An alternative is to take advantage of the efficiency of laser cooling techniques

for atoms: the idea is to cool free atoms in a first step, and then create ultracold

molecules by photoassociation of atomic pairs. This reaction in the cold regime

was first proposed by Thorsheim et al. (1987), and is indeed efficient to form cold

molecules in excited electronic states. Photoassociation has already been demon-

strated for all alkali atoms from Li to Cs: the first studies were for Na2 (Lett et al.,

1993), followed by Rb2 (Miller et al., 1993), Li2 (Abraham et al., 1995), K2 (Wang

et al., 1996), Cs2 (Fioretti et al., 1998), and NaK (Shaffer et al., 1999). Photo-

association has been further demonstrated for hydrogen (Mosk et al., 1999), he-

lium (Herschbach et al., 2000), and very recently for calcium (Zinner et al., 2000),

opening the way to photoassociation of other alkaline earth atoms. However, the

lifetime of a photoassociated molecule is short, and after a few nanoseconds it

decays by spontaneous emission, usually giving back a pair of atoms. The route

to long-lived ultracold molecules depends on the occurrence of particular sta-

bilization schemes in which spontaneous (or stimulated) emission also transfers

population toward bound levels of the ground singlet or triplet state. Theoreti-

cal models have been proposed by Band and Julienne (1995), and by Côté and

Dalgarno (1997, 1999). Other schemes have been found in experiments, and up

56 F. Masnou-Seeuws and P. Pillet

to now long-lived ultracold molecules have been observed for three alkali dimers

Cs2 (Fioretti et al., 1998, 1999; Comparat et al., 2000), K2 (Nikolov et al., 1999,

2000), and Rb2 (Gabbanini et al., 2000). Besides, Takekoshi et al. (1998, 1999)

have observed and trapped ultracold Cs2 molecules formed by a mechanism which

may not be photoassociation and could be three-body collisions. Very recently,

photoassociation experiments in a condensate have also been performed (Wynar

et al., 2000).

The field of cold molecules is experiencing very rapid evolution, both optical

and nonoptical cooling techniques being developed: the fact that it is possible to

write the present review chapter only one year after the previous one is a shin-

ing manifestation of this activity. We may say that spectacular progress has been

accomplished during the last three years in three main directions, two with non-

optical techniques and one with optical techniques.

At present (autumn 2000), the most efficient ways of cooling molecules to a

subkelvin temperatures below 1 K but still above 100 mK, with the perspective of

reaching a few millikelvin in a near future are as follow:

r The helium buffer gas cooling technique developed by the Harvard team

(Doyle et al., 1995; Friedrich et al., 1998, 1999; Weinstein et al., 1998),

together with magnetic trapping of molecules, as already described in the

review of Bahns et al. (2000). CaH molecules, produced via laser ablation of

solid CaH2, are cooled by cryogenic 3He down to a temperature of 400 mK,

and a typical number of 108 molecules are currently loaded in a magnetic

trap (deCarvalho et al., 1999).

r The new Stark decelerator technique introduced by Gerard Meijer and his

group in Nijmegen. They have demonstrated that a beam of neutral dipolar

molecules (CO, ND3) can be decelerated with a time-varying electric field

(Bethlem et al., 1999), bringing them to temperatures down to 350 mK. The

ND3 molecules are then trapped in a traveling potential well (Bethlem et al.,

2000a,b), with a density of ∼106 cm−3 molecules in a volume of ∼0.25 cm−3,

so that the total number of trapped molecules is ∼400,000.

For the formation of ultracold molecules, i.e., at temperatures well below

1 mK, the photoassociation scheme in a sample of laser-cooled ultracold atoms is

presently the best route, yielding a few millions of molecules at a translational tem-

perature in the microkelvin range, which very recently were successfully trapped.

The present review chapter will focus on this subject. The photoassociation re-

action being a crucial step in the process, we shall first review the concept of

photoassociation in Section II, emphasizing the physical ideas behind it. The next

step is the formation of ground-state ultracold molecules by spontaneous emission,

which requires a favorable branching ratio between bound–bound and bound–free

transitions. This is a key point of the experiments, which will be described in

Section III. Then the new theoretical methods developed to interpret such experi-

ments will be described in Section IV. Finally, we shall report on the present status

FORMATION OF ULTRACOLD MOLECULES 57

schemes and the perspectives in the field being discussed in Section VI.

and Formation of Molecules

In photoassociation experiments, first suggested by Thorsheim et al. (1987), a pair

of ultracold ground-state atoms absorbs a photon slightly (∼ a fraction of cm−1 to

1000 cm−1) red-detuned relative to the resonance line. Considering alkali atoms

A(ns), and a laser red-detuned either to the D1 or the D2 resonance line, the reaction

reads

(1)

Hund’s case c representation, hereafter labeled i. This curve is correlated to one

of the two asymptotes (ns + np1/2 ) and (ns + np3/2 ), and 2π ω0 is the frequency

of the corresponding resonance line. hδ L is the energy detuning of the laser and

E c ≃ k B T the kinetic energy of the pair of atoms, where we have introduced

the Boltzman constant k B . In the present review, we shall not consider coupling

between various excited potential curves, and we shall not include effects linked

to the hyperfine structure of the atoms, therefore assuming a detuning larger than

the hyperfine splitting both in the ground state and in the excited state.

From the conservation of energy and angular momentum, taking as the energy

origin the asymptotic energy E(ns + ns) of the ground-state potential, we may

write (Pillet et al., 1997) the resonant condition for population of a bound level

i

with energy E v,J in an electronically excited potential curve i as

i

E c + h(ω0 − δ L ) = E Doppler + E recoil + E v, J. (2)

In Eq. (2), Ec is the kinetic energy associated with the relative motion of the

two atoms, E Doppler = V · hk L is the energy associated with the first-order non-

relativistic effect, and E recoil = (hk L )2 /8μ is the recoil energy. We have introduced

the reduced mass μ of the two atoms, the velocity V of the center of mass, and the

wavevector kL of the laser.

In the following, considering the energy Di of the asymptote of the potential

curve i, we shall often use the binding energy

iv = D i − E i (v, J = 0) = E vi . (4)

58 F. Masnou-Seeuws and P. Pillet

1.4 × 10−5 to 1.4 × 10−4 cm−1 , while in the case of cesium and for a red-detuning

of 1 cm−1 = 29.9792458 GHz, the two other quantities are E Doppler ≃ 100 kHz,

E recoil ≃ 1 kHz.

As we shall see below, since the typical accuracy of the photoassociation ex-

periments is at present of the order of 150 MHz or 5 ×10−3 cm−1, it is justified to

neglect the right-hand side of Eq. (5) and write

hδ L ≈ iv . (6)

energy of the vibrational level and the energy shift of the laser relative to the

resonance line; this is why in photoassociation spectroscopy it is common to use

the word “detuning” for the binding energy iv of a level. This free–bound transi-

tion takes place under conditions somewhat unusual with respect to conventional

molecular spectroscopy:

r Due to the ultracold conditions, the width of the statistical distribution of the

kinetic energy Ec is markedly reduced. For a gas of atoms at thermal equilib-

rium with a temperature T, this width is of the order of k B T . It corresponds

to ∼200 cm−1 at room temperature (300 K), yielding the well-known appear-

ance of diffuse spectra, but only to ∼2 MHz or 7 × 10−5 cm−1, at 100 μK

yielding well-resolved spectral lines, similar to bound–bound transitions. Be-

sides, only a few partial waves have to be considered in the description of

the initial continuum state, so the rotational structure is most often limited

to J < 7–10, in contrast with conventional molecular spectra where a much

larger number of rotational levels are usually observed. The interest of pho-

toassociation as a new spectroscopic technique was reviewed by Stwalley

and Wang (1999).

r In the final state, the vibrational motion extends up to very large internuclear

distances, typically a few tens or even 100 a0. At small detunings, detailed

spectroscopic information has been obtained in the last decade on long-range

molecular states correlated to the (ns + np) dissociation limit of the alkali

dimers, as described in the reviews by Stwalley and Wang (1999) and by

Weiner et al. (1999).

In the present chapter, we shall not describe spectroscopy results but, rather,

concentrate on the determination of the number of molecules formed in a

given experiment. The first question is how many excited molecules are formed

FORMATION OF ULTRACOLD MOLECULES 59

reaction rate, is expected to depend on the electric dipole matrix element be-

tween the wavefunctions in the initial and final states. We shall analyze the final

state and the structure of the excited potential curves with asymptotic −C3i /R 3 be-

havior (see Section II.A). Close to the dissociation limit, vibrational levels in such

potentials can be described with the Le Roy–Bernstein analytical law, presented in

Section II.B, from which we shall deduce scaling laws for various matrix elements.

The theoretical predictions for the photoassociation rate at low laser intensity will

be summarized in Section II.C, and shown to be indeed proportional to the square

of the integral between the wavefunctions in the initial and final states. This inte-

gral will then be estimated by use of the reflection principle (Section II.D): within

a Franck–Condon picture, reaction (1) can be understood as a vertical transition

at a large distance RL = (C3i /hδ L )1/3 from the continuum of the ground state to a

vibrational level of the excited electronic state. In Section II.E, we shall discuss the

variation of the amplitude of the ground-state wavefunction at R = R L , and the

presence of nodes. The efficiency of the photoassociation process will be estimated

(Section II.F) as a function of physical parameters such as the detuning and the

temperature. Then, in Section II.G we shall introduce the problem of controlling

the decay of this short-lived excited molecule into a bound vibrational level of the

ground state rather than into a pair of atoms.

The alkali atoms have been a benchmark for studies of thermal energy collisions,

line broadening, and laser cooling; for alkali dimers, besides the photoassocia-

tion spectroscopy experiments quoted above, there exist much data obtained by

conventional molecular spectroscopy experiments. Therefore the features of the

long-range potentials correlated to the first asymptote have been investigated by

many authors, starting with Dashevskaya et al. (1969), then Movre and Pichler

(1977) as well as Bussery and Aubert-Frécon (1985a, 1985b), Julienne and Vigué

(1991), Marinescu and Dalgarno (1995, 1996), Aubert-Frécon et al. (1998), all of

them quoted in the review of Stwalley and Wang (1999). A few ab initio calcula-

tions exist at shorter distances (Foucrault et al., 1992; Spies, 1989; Magnier et al.,

1993; Magnier and Millié, 1996).

One important feature is the existence of long-range wells: we shall focus on

their particular behavior for the heavy alkali dimers. The concept of a “pure long-

range molecule,” in which the motion of the two atoms is confined to the region

of large distances where only electrostatic interactions are active, any chemical

interaction being negligible, was introduced by Stwalley et al. in 1978.

As an example, we reproduce in Fig. 2 the potential curves for interaction

between two ground-state cesium atoms or, alternatively, a pair of Cs(6s) +

Cs (6 p1/2,3/2 ) atoms. The hyperfine structure being neglected, such figures were

60 F. Masnou-Seeuws and P. Pillet

FIG. 2. Potentials of the Cs2 molecule correlated to the (6s + 6s) and (6s + 6 p 2P1/2,3/2 ) asymp-

totes. Hund’s case c representation is used for the excited potentials, the 2g and 2u curves being not

represented.

obtained by matching the ab initio potential curves from Meyer’s group (Spies,

1989) with the long-range asymptotic expansion of Marinescu and Dalgarno

(1995). Two facts are striking:

r Due to the dipole–dipole R−3 asymptotic interaction, the excited potential

curves extend at much larger range than the ground-state curves with asymp-

totic R−6 behavior. This feature is general for homonuclear dimers, but would

not exist for heteronuclear dimers where the excited curves also display R−6

behavior at long range. Let us note for homonuclear dimers the exception of

i

the 0−g ( p1/2 ) curve for which the C 3 coefficient is zero, so that the asymptote

−6

varies as R .

r Two curves, of 0− g and 1u symmetry, both correlated to the (6s + 6 p3/2 )

asymptote, display a double-well structure, with ∼R −3 behavior in the entire

region of the outer well so that the external side of the barrier has a gentle

slope. Such wells exist for all homonuclear dimers, but we shall see that,

FORMATION OF ULTRACOLD MOLECULES 61

for the heavier ones (Rb2, Cs2), they are located at intermediate internuclear

distances and play a key role in the formation of ultracold molecules. All

symmetries have an exponential short-range repulsive potential for R ≤ 7a0 ,

with a steep slope.

What is the explanation for the existence of those long-range wells? In the

absence of fine-structure coupling, the long-range interaction between a ground-

state atom A (ns) and an atom in the first excited state A (np) is dominated by

the dipole–dipole interaction −C3 /R 3 . As only the excited atom has a permanent

dipole, this interaction corresponds to transfer of excitation between the two distant

atoms. The C3 coefficient is inversely proportional to the radiative lifetime of the

(np) excited atomic level and can be obtained from the square of the dipole moment

matrix element:

This definition is chosen by Julienne and Vigué (1991), and by Marinescu and

Dalgarno (1995). In the work of Aubert-Frécon et al. (1998), all coefficients are

related to a quantity M 2 = |ns|d|np
|2 , which is 3 × C3. The C3 values computed

by Marinescu and Dalgarno (1995) are 5.503 for Li, 6.13 for Na, 8.665 for K, 9.202

for Rb, and 10.47 for Cs. In numerical examples, we note that for the heavy alkalis

C3 is of the order of 10 a.u. In such a model all exchange interaction is assumed

to be negligible, justifying the denomination “a pair of atoms.” Dashevskaya et al.

(1969) have classified the electronic states by their symmetry relative to exchange

of excitation between the two atoms as

ν = (−1) S w, (8)

g and u states, respectively. The long-range dipole–dipole interaction depends on

the orientation of the dipoles relative to each other and to the molecular axis, and

is found to be

C3

+2 for symmetric 1 g+ , 3 u+ states, (→ ←)

R3

C3

−2 3 for antisymmetric 1 u+ , 3 g+ states, (→ →)

R

C3

− 3 for symmetric 1 g , 3 u states, (↑ ↓)

R

C3

+ 3 for antisymmetric 1 u , 3 g states, (↑ ↑).

R

tation, the adiabatic g,u states for a given internuclear distance R at long and

62 F. Masnou-Seeuws and P. Pillet

operator in the subspace of states with the same quantum numbers w and . (As

already stated, we restrict ourselves to distances such that the nuclear spins can be

considered as uncoupled.) Movre and Pichler (1977) have given the secular equa-

tions for all symmetries. This leads, close to the dissociation limit, to asymptotic

coefficients that will hereafter be noted C3i , and are linked by some angular factor

to the C3 coefficient defined above for interaction between an (ns) and an (np)

atom. This angular factor can readily be obtained by considering the asymptotic

expansion of a given i = g,u state on various Hund’s case a states for which

the long-range coefficient is C3 , −C3 , 2C3 , −2C3 according to the symmetry as

described in Eq. (8).

As an example, we shall consider the two 0− −

g ( p3/2 ) and 0g ( p1/2 ) states ob-

tained by diagonalization within the subspace of the (1) g and (1)3 g states.

3 +

For heavy alkali dimers due to the large value of the fine-structure splitting

(E at ( p3/2 )-E at ( p1/2 ) = 237.60 cm−1 for Rb, 554.11 cm−1 for Cs), it is more

convenient to use Hund’s case c representation at all internuclear distances; for

all dimers, the latter representation must be used at large distances to obtain the

correct dissociation limits (ns + np 2 p1/2 ) and (ns + np 2 p3/2 ). At any distance R,

the two 0− g potential curves are obtained (Marinescu and Dalgarno, 1996; Aubert-

Frécon et al., 1998; Fioretti et al., 1999) by diagonalization of the potential matrix

√

E at ( p3/2 ) + 32 V (R) + 13 V (R) 2

" #

3

(V (R) − V (R))

V(R) = √ ,

2

3

(V (R) − V (R)) E at ( p1/2 ) + 13 V (R) + 32 V (R)

(9)

where V (R) and V(R) are the potential curves of the (1) 3 g+ and (1) 3 g

electronic states, displayed in Fig. 3 for Cs2 and both correlated to the (ns + np)

dissociation limit. In Hund’s case c representation, the correct dissociation limits

are obtained at energies E at ( p3/2 ) and E at ( p1/2 ). The coupling between the two

atomic fine-structure levels at finite distance, due to the anisotropy of the mole-

cular potentials, is proportional to the splitting [V (R) − V (R)]. The restriction

to the subspace of states correlated to the (ns + np) asymptote is no longer valid

at small distances.

In the long-range region, where the dipole–dipole interaction dominates, the

V (R) and V(R) curves display their asymptotic −2(C3 /R 3 ) and (C3 /R 3 ) behavior

(see above) and the potential matrix can be approximated by

" √ #

C3 2C3

E at ( p3/2 ) − R3

− R3

V(R) ≈ √ . (10)

2C3

− R3

E at ( p1/2 )

FORMATION OF ULTRACOLD MOLECULES 63

FIG. 3. V (R) and V (R) potential curves (see text) for the Hund’s case a 3 g+ and 3 g states of

the Cs2 molecule. The open circles correspond to ab initio calculations by Spies (1989). Arrows

indicate the distance where the matching with the asymptotic expansion is taking place, choosing

C3i , C6i , C8i coefficients from Marinescu and Dalgarno (1995). In the upper curve, direct matching

being not possible, an interpolation was performed in the region between the two arrows.

The two 0− g asymptotic curves are obtained by diagonalization of this matrix, and

can be considered as R −3 curves with slowly R-varying C3 coefficients. At very

large distances, the upper curve 0− with C3i = C3 ,

g ( p3/2 ) is asymptotically attractive√

while the lower curve is flat (C3 = 0). As the nondiagonal term 2(C3 /R 3 ) is

i

increasing when the atoms get closer,√ there is an avoided crossing at a distance Rmin

3

such that E at ( p3/2 ) − E at ( p1/2 ) ≈ ( 2C3 /Rmin ). This explains why the external

well is located at shorter and shorter distances when the fine-structure splitting

increases from the light alkali atoms (Li, Na) to the heavier ones (Rb, Cs). This

also explains why the repulsive part of this external well, located on the left of this

avoided crossing, is displaying typical R−3 behavior: for R ≤ Rmin , the repulsive

branch of the external well may be approximated by

√ C3

Uup (0−

g ( p3/2 )) ≈ E( p3/2 ) + ( 2 − 1) 3 . (11)

R

For Rb2 and Cs2 molecules, higher-order R−6 and R−8 multipole terms, as well

as asymptotic exchange terms, contribute to the repulsive branch (Aubert-Frécon

et al., 1998; Fioretti et al., 1999), yielding corrections of a few cm−1; nevertheless,

the physics of the long-range external wells is dominated by the dipole–dipole

interaction between a pair of separated atoms. This is why we may say that we

64 F. Masnou-Seeuws and P. Pillet

form “a pair of atoms” rather than a usual molecule; the same idea is expressed in

the concept of a “pure long-range molecule” by Stwalley et al. (1978).

This concept is even more adapted for the long-range well in the 1u ( p3/2 ) curve,

which is located at a distance so large that the hyperfine-structure coupling has to

be explicitly considered. The first observation of a 1u pure long-range molecule

was done by Wang et al. (1998) for K2 (De = 0.5394 cm−1 ) and the Cs2 state was

analyzed recently by Comparat et al. (2000). (see Section III.C)

In contrast, for all attractive curves differing from 0−g ( p3/2 ) and 1u ( p3/2 ) the

vibrational motion extends from large to small internuclear distances, with reflec-

tion on the steep inner barrier. As we shall see later, the time spent in the inner

region is comparatively very short.

WITH RYDBERG LAW, SCALING LAWS

In this section, we shall neglect any rotation effect, assuming J = 0. Let us then

consider a vibrational level with energy E vi close to dissociation limit D i in a

typical i = g,u excited potential curve U i (R) with asymptotic behavior

C3i

U i (R) ≈ D i − . (12)

R3

In the present section we shall also neglect the dynamical coupling with other

channels i, so that the i label can safely be dropped to lighten the notation. A level

will be characterized by its binding energy iv = Di − E vi hereafter denoted v .

However, we shall keep the notation C3i for the long-range coefficient, as it differs

from C3 by an angular factor depending on the symmetry of the curve i.

The vibrational motion takes place both in the long-range region, where the mo-

tion in the asymptotic potential is very slow, and in the short-range region where,

due to the attractive chemical potential, the motion is very quick. Besides, as the

binding energy is negligible compared to the short-range potential, the local de

Broglie wavelength at small internuclear distances is fairly independent of v , so

that this rapid motion is similar for a wide range of levels. As an example, we dis-

play in Fig. 4 two vibrational wavefunctions, for the potential Cs2 (1g , 6s + 6 p3/2 ),

corresponding to binding energies v = 1 and 10 cm−1. Such functions have

been computed according to the numerical method described in Section IV.A. It

is clear that the probability density is concentrated at the outer turning point Rv ,

where the potential can safely be approximated by its asymptotic behavior given in

Eq. (12). This corresponds to the physical idea of two atoms standing still most of

the time at distance R = Rv . A look at the behavior of the two wavefunctions at

small distances, displayed in Fig. 5, confirms that their nodal structure is similar,

the only dependence on the binding energy appearing in their amplitude. This can

FORMATION OF ULTRACOLD MOLECULES 65

FIG. 4. Vibrational wavefunctions in the 1g (6s + 6 p3/2 ) potential of the Cs2 molecule, for two

values of the binding energy, v = 1 and 10 cm−1.

range potential, or alternatively, by the short time spent by the system in the inner

region, leading through the uncertainty relation to a weak energy dependence.

The physical interpretation is thus very similar to the description of the motion

of a Rydberg electron in the potential of an atomic ion, where the effect of the

FIG. 5. Same as Fig. 4, concentrating on the short-range behavior of the wavefunctions for the

two levels with binding energy v = 1 and 10 cm−1. The nodal structure of the two wavefunctions

5/12

is similar, the energy dependence being concentrated on the amplitude, which scales as v , and

therefore increases by ∼2.6 when the detuning is multiplied by 10.

66 F. Masnou-Seeuws and P. Pillet

Rydberg law,

Ryd

E(n, l) = I − , (13)

[n − η(l)]2

linking the energy of a level to the principal quantum number n. In Eq. (13),

I is the energy of the ionization threshold, and Ryd is the Rydberg constant.

The quantum defect is weakly energy-dependent, but depends on the azimuthal

quantum number l.

Considering motion in a potential with power-law asymptotic behavior R−n,

with n ≥ 3, such as in Eq. (12), a generalization of Eq. (13) was derived in 1970

by Le Roy and Bernstein. This law was found to be such an important tool in the

understanding of photoassociation spectroscopy that it seems worthwhile to recall

the main steps of its demonstration (Le Roy and Bernstein, 1970; Stwalley, 1973).

The scaling laws are discussed in the review of Vigué (1982), and the link with

quantum defect theory analyzed by Ostrovsky et al. (2001).

Assuming the semiclassical picture to be valid, the vibrational wave function for

a bound level with energy E v in the single potential U(R) may be written (Landau

and Lifshitz, 1977) as

R

1 1

v (R) = Nv sin k(R ′ ) d R ′ + π , (14)

k(R) v

Rin 4

Rv

′ ′ 1

βBS (E v ) ≡ k(R ) d R = v + π. (15)

v

Rin 2

v

In Eqs. (14) and (15), Rin and Rv are, respectively, the inner and outer turning points

of the vibrational motion. For a diatomic system with reduced mass μ, we have

defined the local wavenumber kv (R) and local de Broglie wavelength λv (R) as

1 2π

kv (R) = 2μ[E v − U (R)] = . (16)

h λv (R)

Therefore Eq. (14) is not valid close to a classical turning point, where

v

kv (Rin ) = kv (Rv ) = 0. We shall give below a more general expression that is also

valid close to a turning point. The normalization factor is linked to the classical

period of motion (Landau and Lifshitz 1977) through

Rv

d R′

hTvib

2[Nv ]−2 = ′

= , (17)

v

Rin kv (R ) 2μ

FORMATION OF ULTRACOLD MOLECULES 67

where Tvib is defined as the time necessary to go from the outer turning point to

the inner one and back. The physical explanation given by Lefebvre-Brion and

Field (1986) is that the probability amplitude in Eq. (14) is linked to the classical

probability density, which is inversely proportional to the velocity times the period.

From differentiation of the Bohr–Sommerfeld condition (15) over the quantum

number, the same integral gives the inverse of spacing between the levels,

Rv

d R′

π

dv

h 2

= . (18)

μ d E E=Ev

v

Rin k(R ′ )

From this an important relation between the normalization factor and the level

spacing,

π h2 2

d E v

= N , (19)

dv E=Ev

2μ v

For highly excited vibrational levels, the integral in Eqs. (15) and (18) is de-

termined mostly by the outer domain of distances R, where the potential can be

approximated by the general asymptotic formula U (R) = D − Cn /R n ; this al-

v

lowed Le Roy and Bernstein (1970) to evaluate it in the limit Rin /Rv → 0 with an

analytical formula,

Rv

d R′ 2n π h 2

′

= (D − E v )−(n+2)/2n , (20)

v

Rin k(R ) n − 2 2μHn

2π (n − 2) Ŵ(1 + 1/n) −1/n

Hn = h Cn . (21)

μ 2Ŵ(1/2 + 1/n)

Rydberg law to any potential in R −n , n = 2,

threshold divided by π . We may define an effective quantum number,

veff = v D − v, (23)

such that the levels are now numbered starting from the dissociation limit. In the

spirit of the quantum defect theory (Seaton, 1983; Friedrich, 1998) it can be shown,

as illustrated in Fig. 5, that for levels close to the dissociation limit, the wavefunc-

tions exhibit the same nodal structure at short distances, the energy dependence

68 F. Masnou-Seeuws and P. Pillet

being concentrated in the normalization factor. Therefore any change in the short-

range potential results into a modification of the phase in Eq. (15) equivalent for

all such levels: whereas the total phase πv D is modified, the difference π (v D − v)

remains a constant.

In the case of photoassociation into an excited curve with long-range R −3

behavior as described by Eq. (12), the law giving the dissociation energy reads,

using Ŵ(4/3)/ Ŵ(5/6) = 0.790903 = γ3 and

$

π i −1/3 −1/3

H3 = 0.790903h C3 = A3 C3i , (24)

2μ

and considering the cesium dimer, with C3i ≈ 10 a.u. and atomic mass M A = 133

as a reference,

133 3 10 2

v = H36 (v D − v)6 = veff

6

× 1.17 10−12 cm−1 , (25)

MA C3i

where M A is the atomic mass so that μ = 1822.8885(M A /2). Close to the dis-

sociation limit there is a quasi-continuum of vibrational levels: for a detuning of

1 cm−1, the numbering of a Cs2 level from the dissociation limit is already ∼100!

This is why it is more convenient to analyze the present vibrational series by con-

sidering an energy scale rather than a numbering of levels. For a given dimer, the

vibrational progression in Eq. (25) is a signature of the excited electronic state i

populated by photoassociation, through the C3i coefficient. The vibrational spacing

rapidly increases as a function of detuning, according to

d E

dv

=− = +6(H3 )6 (veff )5 = −6H3 (v )5/6 . (26)

dv E=Ev

dv

We can give an estimate of the level spacing taking the cesium dimer as reference,

1/3

dv

−2 133 10

= −6.14 × 10 (v )5/6 cm−1 . (27)

dv

E=Ev M A C3i

In the case of Cs2, choosing C3i = 10.47 from Marinescu and Dalgarno (1995),

the level spacing is increasing from ∼0.06 to ∼0.4 cm−1 when the detuning varies

from 1 to 10 cm−1. The classical outer turning point,

1/3

C3i

Rv = , (28)

v

then decreases from 131.9 to 61.5 a0, verifying a (v )−1/3 or (veff )−2 scaling law,

which, we shall see later, clearly manifested in the photoassociation spectra. The

FORMATION OF ULTRACOLD MOLECULES 69

scaling law verified by the normalization factor in Eq. (19), may be deduced from

the vibrational spacing,

2 −2 M A dv

−1

. (29)

133 dv E=E v

We can verify in Figs. 4 and 5 that the inner part of the wavefunctions is in-

deed scaled by a factor ∼2.6 when the detuning is varying from 1 to 10 cm−1,

corresponding to a change of (Nv )2 by a factor 105/6 ≈ 6.8. As this (Nv )2 normal-

ization factor scales any matrix element of a physical quantity corresponding to

short-range coupling, the (veff )5 or (v )5/6 scaling law is then equivalent to the

well-known ν −3 scaling law for Rydberg states (Seaton, 1983; Friedrich, 1998).

We should mention that in the case of an asymptotic R −5 potential, Gouédard

et al. (1989) gave for the first time experimental verification of the corresponding

scaling law near a dissociation limit of the Cl2 molecule.

The formation of ground-state molecules in low enough vibrational levels can

be considered as a short-range process, as it involves the overlap with short-

range vibrational wavefunctions in the ground state. Therefore, the corresponding

5/6

probability is expected to scale as v as a function of the binding energy, and

5/6

hence as δ L as a function of detuning. Thus, large detunings are expected to be

more favorable. In contrast, we shall see later that, the photoassociation process is

definitely more favorable at small detunings.

It is also interesting, within a time-dependent picture, to estimate the classical

vibrational period in the (ns + np) excited potential curve of a dimer A2,

1/3 $

C3i [a.u.]

MA

Tvib [ps] ≈ (v [cm−1 ])−5/6 × 534 ps. (30)

10 133

Assuming C3i values around 10 a.u., and for a 1-cm−1 detuning, the vibrational

period has a magnitude of about 500 ps. At even smaller detunings, this classi-

cal vibration period becomes of the order of magnitude of the radiation lifetime

(a few nanoseconds), so that a model neglecting spontaneous emission is no longer

valid, and time-dependent models must be implemented.

To be through, we should give a correct expression, thorough for the semi-

classical wavefunction in the vicinity of a turning point, where the approximation

given in Eq. (14) is no longer valid. We shall follow the derivation proposed by

Vigué (1982), Lefebvre-Brion and Field (1986), and Child (1991) and write the

uniform semiclassical (USC) wavefunction (Miller, 1968), valid for all values of

R, as

1/4

N Z (R)

vUSC (R) = √ Ai[−Z (R)], (31)

π k(R)2

70 F. Masnou-Seeuws and P. Pillet

where

% R we have introduced an Airy function of the phase Z (R) =

[ 32 R v k(R ′ ) d R ′ ]2/3 . The sine behavior as a function of the phase is reached

in

for Z > 1.5, where the uniform semiclassical function becomes equivalent to the

sine function

√ in Eq. (14). The factor multiplying the Airy function in Eq. (31) is

then N π(h[Rv ]2 )1/3 [6μC3i ]−1/6 , where Rv is the outer turning point linked to

the detuning through Eq. (28).

The semiclassical arguments developed in the present section, the choice for

the norm, and therefore the derivation of the scaling laws, are no longer valid

close to the dissociation limit, when the wavefunction has an important extension

in the nonclassical region and behaves as an evanescent wave. Corrections to the

semiclassical model have been proposed by many authors, and will be discussed in

Section IV.A.3. Such corrections concern very few levels close to the dissociation

limit. Bendes numerical calculations are available in all cases.

Scaling laws offer an invaluable tool in the interpretation and fitting of experi-

ments: the Le Roy–Bernstein formula has been widely used in order to identify

the excited electronic states or to fit C3i coefficients to the observed spectrum [see

the review of Stwalley and Wang (1999), and references therein]. Examples will

be given in Section III.C.

Generalization of the present derivation to two coupled channels has been pro-

posed recently by Kokoouline et al. (2000a) and Ostrovsky et al. (2001). The

energies of the levels for two coupled vibrational series can be plotted as Lu Fano

plots and fitted by three parameters, which are two generalized quantum defects

and a reduced coupling parameter.

The problem is to estimate how many excited molecules in a given ro-vibrational

level will be created in a photoassociation experiment. Many different groups have

been working on the theory of photoassociation, using both “time-independent”

formalism, with stationary wavefunctions (Napolitano et al., 1994; Pillet et al.,

1997; Côté and Dalgarno, 1998; Mackie and Javanainen, 1998), and “time-

dependent” formalism, with wavepacket propagation (Mackholm et al., 1994;

Vardi et al., 1997; Boesten et al., 1999; Vala et al., 2001; Vatasescu et al., 2001).

After some controversy, there is presently agreement between various approaches

for “time-independent” calculations. Up to now, “time-dependent” calculations

have focused on the presentation of new schemes rather than quantitative predic-

tion of the photoassociation rates, and will be described in Section VI. A precise

comparison between the predictions of “time-dependent” and “time- independent”

approaches is still lacking.

The quantum formulation of the transition between a bound level and a contin-

uum level of a molecule due to coupling by the electromagnetic field between two

FORMATION OF ULTRACOLD MOLECULES 71

electronic states was considered in the early days of quantum mechanics (Condon,

1928; Winans and Stueckelberg, 1928; James and Coolidge, 1939) using various

approximations. Doyle (1968) has given a detailed derivation of the absorption co-

efficient in a sample of hydrogen atoms: the rate is then defined as the probability

of absorption of a photon for an incident beam of one photon crossing unit area

per second and per unit frequency interval.

Napolitano et al. (1994) as well as Côté and Dalgarno (1998) use this definition

to compute the absorption rate coefficient for the inelastic process yielding a bound

molecule out of two ground-state 2S alkali atoms via absorption of a photon with

energy hω L = h(ω0 − δ L ) according to the reaction (1)

∞

2 πh 2

K (T, ω L , v) = (n at ) (2J + 1)|S(E, J ; i, v, J ; ω L )| (32)

k J =0

amplitude between the initial continuum level at energy E and a bound level v, J in

the excited potential curve i. Here, . . . . . . . . . is an average over the distribution

of initial velocities. If a Maxwellian distribution at temperature T is assumed,

expression (32) yields for the absorption coefficient

∞

n2 ∞

K (T, ω L , v) = (2J + 1) at × d E e−E/kT |S(E, J ; i, v, J ; ω L )|2 ,

J =0

h QT 0

(33)

where the translational partition function Q T = (2π μk B T / h 2 )3/2 has been intro-

duced. In most papers, the numerical results are given for the quantity K (T, ω L , v)

divided by the incident photon flux and by the square of the atomic density.

Various approximations have been discussed to simplify the calculations. Al-

though the S-matrix element has to be computed by solving coupled equations,

Napolitano et al. (1994) show that their close-coupling calculations for sodium, in

a temperature range from 0.01 to 10 mK, can be approximated by a very simple

resonant scattering expression involving the width of the bound level defined as a

function of the spontaneous emission rate and the stimulated emission rate back

to the ground state. Such expression is similar to a Breit–Wigner formula, and

Gardner et al. (1995) have generalized it taking account of the directional depen-

dence. Photoassociation can then be viewed as an optically induced Feshbach reso-

nance, and the richness of this point of view has been recently demonstrated by the

experiments of Fatemi et al. (2000), who measured such resonances in a sodium

sample. At low laser intensities, in the framework of a perturbative treatment, the

widths factors in the Breit–Wigner formula involve the electronic transition mo-

ment between the unperturbed initial and final states. In the present work we shall

72 F. Masnou-Seeuws and P. Pillet

not discuss the shape of the photoassociation lines, assuming that the resonance

condition(s) can be expressed by a δ function. By use of a Fermi-golden-rule type

of approximation, Côté and Dalgarno (1998) find

I

& '

2

S(E, J ; i, v, J ; ω L ) ∼ 8π 3

ψ E,J (R)|D(R)|φv,J

i

(R)

δ(E − hδ L + v ),

c

(34)

where we have introduced the coupling matrix element, proportional to the square

root of the laser intensity and to the molecular transition dipole D(R), between the

energy normalized ground-state scattering wavefunction ψ E,J (R) and the unper-

i

turbed vibrational function ψv,J (R). With an R-centroid approximation (Lefebvre-

Brion and Field, 1986), the electronic transition moment can be further approxi-

mated by

& i

' &

i '

ψ E,J (R)|D(R)|φv,J (R) ≈ D(Rv ) ψ E,J (R)

φv,J (R) , (35)

i.e., the product of D(Rv ), value of the dipole moment at the outer classical turning

point of the vibrational motion, and the overlap integral, the square root of the

Franck–Condon factor. Therefore, for a laser tuned at resonance, the photoas-

sociation rate is controlled by the Franck–Condon factor between the radial wave

functions in the initial continuum level and the final bound level.

The approach developed by Pillet et al. (1997) uses an atomic physics point

of view and a density-matrix description of a collection of N atoms, interacting

by two-body interaction, in the presence of laser light at time t. The density ma-

trix at time t = 0 is computed for an assembly of atoms when the laser is off,

assuming a Maxwell–Boltzmann distribution at temperature T. The coupling ma-

trix element is described by a δ function approximation in the spirit of Eq. (34),

considering that the rotational quantum number may vary between the initial and

final states. The time evolution equation of the density matrix, in interaction rep-

resentation, is solved in a perturbative approach. For a low intensity I of the pho-

toassociation laser tuned at resonance, the photoassociation rate RPA (in s−1),

defined as the number of photoassociated molecules, formed in an individual level

(v, J), divided by the total number Nat = n at V of atoms in a trap of volume V , is

found as

3/2

3 h

′

RPA = A(J, J , ǫ P A ) n at λ3th

2π 2

−Er '

2

K 2

ψ E,J (R)

φv,J

&

i

× exp ′ (R)

, (36)

kB T

FORMATION OF ULTRACOLD MOLECULES 73

where A(J, J ′ ), ǫPA )is an angular factor depending on J, J ′ and on the laser

polarization. λth = h 1/(3μk B T ) is the thermal de Broglie wavelength, and 2K

is the atomic Rabi frequency. The latter is a function of the laser intensity I,

Ŵ I

K2 = , (37)

8 I0

width of the atomic np level, Ŵ/2π . In the case of cesium, Ŵ/2π = 5.22 MHz,

so the saturation intensity has a value of 1.1 mW/cm2 at the PA laser wavelength

λPA = 2πc/ω0 . The rate RPA in Eq. (36), divided by n at and by the incident photon

flux φ = I /hωPA yields a rate κ per photon and per unit density (its dimension is a

length to the fifth power), which is similar to the expressions given by most other

authors (Napolitano et al., 1994; Julienne, 1996; Côté and Dalgarno, 1998). The

quasi-continuum approach developed by Javanainen and Mackie (1998), Mackie

and Javanainen (1999) avoids the use of delta functions and yields a similar result.

OF FRANCK–CONDON FACTORS

The estimation of the photoassociation probability thus relies on knowledge of the

Franck–Condon factor,

'

2

F(E ∼

&

i

= k B T, J ; i, v, J ′ ) =

ψ E,J (R)

φv,J ′ (R)

. (38)

In the following we shall consider J = J ′ and drop the angular factor A(J, J ′ , ǫPA ).

Optical transitions between a bound and a continuum level of a molecule were

studied in the early days of quantum mechanics and viewed as vertical transi-

tions, at a given internuclear distance, between two electronic states (Franck,

1925; Condon, 1926, 1928). In his review on the Franck–Condon principle in

bound–free transitions, Tellinghuisen (1985) gives an extensive discussion of the

various approaches to the problem, through classical, semiclassical, or quantum

methods.

In a semiclassical approach, the overlap integral can be estimated within a

stationary phase approximation. Such a procedure, derived by Jablonski (1945),

has been adapted to the photoassociation problem by Julienne (1996), and further

discussed by Wang and Stwalley (1998) and Boisseau et al. (2000b). The main

idea of this derivation is to write the product of two oscillating functions as the

sum of two functions, and to neglect the high-frequency component, in order

to keep only the low-frequency term. The approach is valid provided the two

wavefunctions oscillate at frequencies that are not too different, so that the sum of

74 F. Masnou-Seeuws and P. Pillet

the frequencies is indeed much larger than their difference. When the continuum

function is oscillating much more slowly, i.e., at very low temperatures, Pillet et al.

i

(1997) consider for the vibrational function in the excited potential φv,J (R) an Airy

function behavior in the vicinity of the outer classical turning point. We shall see

later that the same formula is obtained by the two methods. The Franck–Condon

factor obtained with the stationary-phase method is

i

d E v,J 1

F(E, J ; i, v, J ) ≈ i

i

|ψ E,J (Rv,J )|2 , (39)

dv D Rv,J

i i

proportional to the value ψ E,J (Rv,J ) of the continuum wavefunction at R = Rv,J ,

in accord with the image of a vertical transition where the vibrational motion is

stopped. We shall use this formula for J = 0, and drop the J index hereafter.

The level spacing is introduced because of the normalization factor in the

vibrational wavefunction [see Eq. (19)], while, as in the Landau–Zener formula,

the quantity D(Rvi ) is the difference between the slopes of the two potential curves

at R = Rvi ,

d

D Rvi = [U i (R) − Vg (R)]| R=Rvi ,

(40)

dR

point Rvi has been defined in Eq. (28). Vg (R) is the ground-state potential, which

g

in the asymptotic region behaves as ∼−C6 /R 6 and therefore exhibits a much

i

weaker slope than the excited potential U (R). We may write

i 4

1 R 1 1/3

≈ v i ≈ C3i (v )−4/3 . (41)

D Rvi 3C3 3

A look at Eq. (39) shows that, as far as the choice of the final bound level is

concerned, the efficiency of the photoassociation reaction involves the competition

of two effects:

r In order to optimize the difference of slopes, which scales as (v )−4/3 , or

(Rvi )4 , the photoassociation process should take place at small detunings,

corresponding to a Condon point Rvi located at large distances, where the

two curves have similar slopes.

r In contrast, the normalization factor for the vibrational level v, related to the

level spacing d E vi /dv, scales as (v )5/6 , or (Rvi )−5/2 , so that if we keep the

FORMATION OF ULTRACOLD MOLECULES 75

when photoassociation is taking place at large distances Rvi .

The competition of these two effects gives a (v )−1/2 dependence on the detuning.

Of course, the Franck–Condon factor also depends on the behavior of the ground-

state wavefunction, which, as discussed in the next section, favors excitation at

small detunings, or vertical transition at a large distance Rvi .

SCATTERING WAVEFUNCTION

From Eq. (39), we see that the Franck-Condon factor reflects the nodal structure of

the ground-state continuum wavefunction, in the sense that the s-wave contribution

to the photoassociation signal will be zero when the Condon distance Rvi is such

that ψ E (Rvi ) = 0. We display, in Figs. 6 and 7, an example of the wavefunctions

ψ E (R) describing s-wave scattering of two ground-state cesium atoms, interacting

through the ground X1 g+ or lower-triplet a 3 u+ potential, for a collision energy of

FIG. 6. Energy-normalized wavefunction E (R) for scattering of two ground-state cesium atoms

in the X1 g+ potential at a temperature of 140 μK. The computed wavefunction corresponds to a

ground-state scattering length a S = −33a0 . The two arrows indicate the distances Rvi = 131.9 a0 and

Rvi = 61.5 a0 corresponding to photoassociation at detuning v = 1 and 10 cm−1, respectively, for an

excited potential varying asymptotically as −C3i /R 3 , with C3i = 10.47 a.u.

76 F. Masnou-Seeuws and P. Pillet

FIG. 7. Energy-normalized wavefunction E (R) for scattering of two ground-state cesium atoms

in the a 3 u+ potential at a temperature of 140 μK. The computed wavefunction corresponds to a

negative scattering length aT = −530a0. The two arrows indicate the distances Rvi = 131.9a0 and

Rvi = 61.5a0 corresponding to photoassociation at detuning v = 1 and 10 cm−1, respectively, for an

excited potential varying asymptotically as −C3i /R 3 , with C3i = 10.47 a.u.

140 μK. The scattering lengths were chosen a S = −33a0 from Dion et al. (2001)

and aT = 530a0 from Drag et al. (2000b). The main feature is the existence of two

very different regions:

r At long range, when the ground-state potential is negligible, the wavefunction

has sine behavior, with anamplitude inversely proportional to the square root

of the wavenumber k = (2μE/h 2 ) (or to E 1/4 ) and a phase depending on

the scattering length a S,T ,

1/4

2μ

E (R) = sin[k(R − a)]. (42)

π h2 E

2

lision energies as E −1/2 . If the scattering length is positive, a minimum

in the photoassociation signal is observed for a Condon point located at

distance a.

r At very low temperature, the Wigner threshold law behavior is reached, and

in the asymptotic region E (R) is approximated by linear behavior as a

FORMATION OF ULTRACOLD MOLECULES 77

1998),

$

2μ R

0 (R) ≈ 2

sin[δ0 (k)] − 1 + O(k 2 ) (43)

πh k a

$

2μk a

≈ 2

R 1− , (44)

πh R

0

r At shorter distance, due to the presence of the ground-state potential and

to quantum reflection effects, the amplitude of the wavefunction E (R) is

dramatically decreased, leading to a loss of more than one order of magni-

tude in the photoassociation efficiency, and to the existence of minima in

the photoassociation signal reflecting the nodal structure in the ground-state

wavefunction. Such minima, predicted by Côté and Dalgarno, were observed

for the first time by Hulet’s group (Côté et al., 1995) and then in many

photoassociation experiments (Julienne, 1996), leading to accurate determi-

nation of the scattering length (Drag et al., 2000b).

r First, the bottleneck in the photoassociation probability lies in the amplitude

of the ground-state wavefunction, which depends on the scattering length

and increases at low collision energies. It is more efficient to implement pho-

toassociation in the long-distance region where the continuum wavefunction

has reached asymptotic behavior. For instance, in the example of cesium

photoassociation chosen in the present review, we may see in Figs. 6 and 7

that by increasing the detuning from 1 to 10 cm−1, Rvi is decreasing from

131 gao to 61.5 ao and the amplitude of E (Rvi ) decreases by one order

of magnitude, and hence the photoassociation probability decreases by two

orders of magnitude.

r Second, accurate calculations of the overlap integrals should be performed,

the analytical formulas being helpful only to estimate the orders of magni-

tude in the low-detuning region, for temperatures low enough that the linear

approximation of the wavefunction in Eq. (44) is valid. We shall describe

accurate numerical methods in Section IV.A.

The perturbative approach adapted to the weak laser-field regime, developed by

Pillet et al. (1997), may be used for the calculation of photoassociation rates as

78 F. Masnou-Seeuws and P. Pillet

following. In a region where the ground-state potential is negligible, and at very

low energies, the wavefunction E (R) can be approximated by a linear variation,

so that the Franck–Condon factor may be written from Eqs. (39) and (12) as

a 2

4γ3 2/3 −7/6

F(E, J = 0; i, v, J = 0) ∼ √ 2 C3i v μE 1/2 1 − , (45)

πh Rv

which is equivalent to the formula given by Wang and Stwalley (1998), in a paper

where they compare homonuclear and heteronuclear systems. From Eqs. (19), (39)

−7/6

and (41) one may predict for the overlap integral a dependence in v , since

the linear increase of the ground-state wavefunction as a function of distance R

−2/3

is introducing an extra v factor. The E1/2 energy dependence is linked to the

linear approximation of the wavefunction, and would change to a E −1/2 depen-

dence if the asymptotic sine behavior of Eq. (42) was considered for the initial

continuum wavefunction. Using Airy function representation for the excited-state

wave function, as in the work of Pillet et al. (1997), the same formula is obtained

for the estimation of the Franck–Condon overlap by analytical integration of the

product of an Airy function and a sine function. Care must be taken to use the

normalization of the vibrational wavefunction defined in Eq. (31), which is a fac-

tor 1.29 larger than the norm used by Pillet et al. (1997) from linearization of the

potential. Numerical tests of the validity of the estimation in Eq. (39) are presented

by Pillet et al. (1997) and by Boisseau et al. (2000b). In the latter case, the va-

lidity range of the reflection approximation is extensively discussed, and overlap

integrals for p and d waves are given as well as for s waves. The conclusion is

that the reflection approximation is valid in a large domain of physical situations,

justifying the present discussion.

The conclusion of the paragraph is that photoassociation is much more efficient

at large internuclear distances or at small detunings, creating excited molecules

in loosely bound vibrational levels, which most of the time look like a pair of

two atoms at large distance Rvi . This molecule, being in an excited electronic

state, decays by spontaneous emission, the lifetime being of the order of a few

nanoseconds.

OR LOWER TRIPLET STATE

The next problem is how to use those short-lived photoassociated molecules to cre-

ate long-lived molecules in a bound level v0 of the ground state or lower triplet state.

The spontaneous emission process is most likely to take place through vertical tran-

sition at a large distance Rvi . As the ground potential curves, with R−6 asymptotic

FORMATION OF ULTRACOLD MOLECULES 79

behavior, display a much narrower well (see Fig. 2), the vibrational motion does

not extend that far, so spontaneous decay populates mainly continuum levels, and

eventually a few of the uppermost bound levels. Once a photoassociated molecule

is formed, it usually decays back into a pair of free ground-state atoms,

(46)

both atoms to escape from the trap, so most photoassociation experiments have

indeed been analyzed through trap-loss measurements.

In order to make ground-state molecules, several schemes have been proposed

by theoretical goups. Côté and Dalgarno (1997, 1999) discuss how spontaneous

decay of the photoassociated molecule populates the uppermost vibrational levels

of the ground state.

+

(ns + ns; v0 , J )] + h(ω0 + δ3 ).

(47)

Their study for one excited potential curve of Li2 confirms that the branching ratio

between reactions (47) and (46) is very low, leading to a small population transfer

into the last least-bound level of the ground X 1 g+ state, which is hardly a bound

molecule. A similar conclusion has been obtained recently in the Cs2 case by Dion

et al. (2001). Therefore, Côté and Dalgarno (1997, 1999) propose implementing

a Franck–Condon pumping scheme in order to transfer the population to lower

vibrational levels. They consider sequences with absorption of laser light to a

lower and lower vibrational level v1 < v of the A1 u+ or 13 g+ excited potential

curves, followed by spontaneous emission. Detailed calculations of the absorption

and spontaneous emission probabilities show that a large part of the population is

lost at each step by spontaneous emission to the continuum [reaction (46)], and

the authors conclude that the scheme is not efficient unless induced emission is

considered instead of reaction (47).

Another scheme was proposed by Band and Julienne (1995), who suggested a

two-photon sequence in which the photoassociation step is followed by absorption

to a Rydberg state with good Franck–Condon overlap with low vibrational levels

in the ground state. This scheme was implemented for K2 in the experiments of

Nikolov et al. (1999), and we shall see discuss its efficiency later.

Long-lived ultracold molecules were first observed in the cesium photoassocia-

tion experiment of Fioretti et al. (1998), owing to a formation scheme that was not

originally considered by the theoreticians, and is clearly linked to the particular

features of long-range wells in heavy alkali dimers. Indeed, we shall show that an

80 F. Masnou-Seeuws and P. Pillet

efficient mechanism has been found in situations where the vibrational motion of

the photoassociated molecule is gradually slowed down at intermediate distances,

leaving the possibility for vertical transition into a bound level of the ground

(or lower-triplet)-state potential curve.

A. INTRODUCTION

In this section, we present the experimental results for the formation of ultra-

cold molecules via photoassociation of laser-cooled atoms in a magnetooptical

trap device (MOT). We give a detailed description of the experimental scheme in

Orsay that led to the first observation of ultracold molecules in cesium (Fioretti

et al., 1998). Compared to the photoassociation spectroscopy experiments, the

cold molecule experiments differ by the direct detection of the formed molecules,

based on a photoionization process coupled with a time-of-flight mass spectrom-

eter. Most of the time, the states studied in the photoassociation experiments do

not give formation of cold molecules. This is due to the very weak branching ratio

in favor of bound–bound transitions from the excited photoassociated molecules,

which generally dissociate after spontaneous emission of one photon. We analyze

carefully the mechanisms of formation of cold molecules in the case of cesium

atoms, which are particularly efficient, making the cesium dimer a quite ideal

case. We expose the precise measurements for the translational temperature in the

molecular sample and for the rate of cold-molecule formation. We present finally

the recent demonstration of the stimulated Raman photoassociation process to

prepare state-selected cold molecules, so opening the way to the preparation of

molecules, not only translationally cold but also vibrationally and rotationally cold.

We discuss the other experimental schemes (Nikolov et al., 1999, 2000; Gabbanini

et al., 2000). We briefly present the possible developments for trapping the formed

cold molecules and analyze the experiment using a CO2 laser quasi-electrostatic

trap by Takekoshi et al. (1998). Finally, we mention very briefly the formation of

cold molecules in a condensate (Wynar et al., 2000), a subject which exceeds the

frame of this review.

A scheme of the setup is shown in Fig. 8. Photoassociation (PA) experiments with

cold alkali atoms are performed with the usual tools for providing cold atomic

samples: a magnetooptical trap (MOT) (Raab et al., 1987; Monroe et al., 1990),

FORMATION OF ULTRACOLD MOLECULES 81

√ setup. (b) Detection time sequence. The Cs+ and Cs+

2 ion

pulses arrival times are in a ratio 2. (c) Overlap between the PA laser beam and the cold atomic

sample.

dark SPOT (dark spontaneous force optical trap) (Ketterle et al., 1993; Townsend

et al., 1996), or a dipole trap such as FORT (far off-resonance trap) (Miller et al.,

1993.) Very recently, PA experiments have also been developed by using a rubidium

condensate (Wynar et al., 2000). In the cesium experiments, the cold atom source

is provided by the use of either a Cs vapor-loaded MOT or a dark SPOT. Details of

the experimental setup have been published in several previous articles (Comparat

et al., 1999). Using a dark SPOT instead of a MOT implies a different initial state

of the pair of atoms in the PA collisional process: the atoms are in the 6s1/2 , f = 3

hyperfine level, instead of being in f = 4.

In a vapor-loaded MOT, the cold Cs atoms are produced at the intersection of

three pairs of mutually orthogonal, counterpropagating σ + – σ − laser beams of

intensity 1–2 mW/cm2 and of diameter 6 mm, at the zero magnetic field point

82 F. Masnou-Seeuws and P. Pillet

The residual pressure is 2 ×10−9 torr. The cooling and trapping laser beams are

split from a slave diode laser (SDL 5422-H1, 150 mW, single mode, λ ≈ 852 nm)

injection locked to a master diode laser. The master laser (SDL 5412-H1, 100 mW)

is stabilized by optical feedback from an extended, grating-ended cavity. Locking

the master laser frequency to a saturated absorption line of a cesium vapor ensures

its long-term stabilization. The trapping laser frequency is tuned about 13 MHz

(≃2.5 natural linewidths) on the red of the frequency ν 4→5 of the 6s1/2 , f =

4 → 6 p3/2 , f ′ = 5 atomic transition (see Fig. 1, left). A repumping laser beam

(SDL 5712-H1, 100 mW, λ ≈ 852 nm) of frequency ν 3→4 resonant with the

61/2 , f = 3 → 6 p3/2 , f ′ = 4 transition is superimposed with two of the beams of

the cooling laser, preventing atoms from being optically pumped in the untrapped

f = 3 hyperfine level of the ground state. The total number of cold atoms inside

the trap is determined by using a calibrated photodiode to record the fluorescence

signal due to the trapping laser. We use the expression for the detected power of

fluorescence in the solid angle , given by

Ŵ C12 ωtot

2

/2

P = Nat hνtrap . (48)

4π 2 δ 2 + Ŵ 2 /4 + C22 ωtot

2

/2

In Eq. (48), ωtot is the total Rabi frequency due to the six trapping laser beams at

the frequency ν trap, Ŵ is the inverse of the characteristic time of spontaneous emis-

sion. C1 and C2 correspond to effective coefficients, C12 ≃ C22 ≃ 0.73, measured

experimentally by Townsend et al. (1995). These coefficients do not correspond to

those expected (≃0.4) by assuming an equirepartition on all the Zeeman sublevels

of the atomic ground state f = 4. They indicate a larger population in the magnetic

sublevels with maximum absolute quantum numbers.

Depending on the experimental conditions (laser detuning and intensity), the

number of atoms lies in the range between 2 and 5 × 107 and the temperature T

of the cold atomic sample ranges between 20 and 200 μK (Fioretti et al., 1999).

For a detuning of 14 MHz, an intensity of ∼1 mW/cm2 for each laser beam, and

a temperature of 140 ± 20 μK, the number of atoms is Nat of 4.7 × 107 estimated

within a factor of 2. The atomic sample is approximately spherical. We assume

that the density is proportional to a gaussian distribution exp(−r 2 /2σ R2 ), with

σ R = 300 ± 50 μm in the three space dimensions. The mean density is of the

order of 4 × 1010 atoms/cm3 (∼1011 atoms/cm3 for the peak density) and is known

within a factor of 3. In these experimental conditions, the characteristic loading

time for the trap has been measured in the range 600–800 ms, depending on day-

to-day fluctuations of the experimental conditions. In the MOT and dark SPOT

devices, atoms can be further cooled below the Doppler limit, down to T ≤ 30

μK, by detuning, during 7 ms, the trapping laser to nine natural linewidths and

simultaneously reducing the beam’s intensity by a factor of 2 through a Pockels

FORMATION OF ULTRACOLD MOLECULES 83

cell. The MOT is shifted into a dark SPOT configuration by modifying the re-

pumping arrangement to transfer most of the atoms (>90%) in the “dark” state

f = 3 in the center of the trap. The repumping beam is now partly screened with

a 3-mm-diameter black spot of insulating tape, stuck onto a microscope slide. The

spot is imaged at the center of the trapping region using a lens of focal length

l = 400 mm, placed at a distance 2l apart. Just after the lens, a beam splitter splits

the repumping laser beam into two beams. They are superimposed with two cool-

ing laser beams. The images of the spot for the two laser beams correspond to the

center of the trapping zone. The difficulties in applying the dark SPOT technique to

heavy atoms have already been noticed (Townsend et al., 1996). To obtain a large

fraction of the atoms in a “dark” state, we illuminate the cold atomic sample with

a depumping laser beam of about 10 mW cm−2, tuned about 25 MHz (∼5 natural

linewidths) on the blue of the frequency ν 4→3 of the 6s1/2 , f = 4 → 6 p3/2 , f ′ = 3

atomic transition. For that purpose, the diode laser is locked on the level cross-

ing 6s1/2 , f = 4 → 6p3/2 , f ′ = 3 and 6s1/2 , f = 4 → 6p3/2 , f ′ = 5 and the laser

beam passes through an acoustooptic modulator which shifts its frequency by

200 MHz. We have verified by photoabsorption that more than 90% of the atoms

in the center of the trapping zone are in the “dark” state f = 3.

2. Photoassociation Laser

The trapped, cold Cs atoms are illuminated with a continuous-wave (CW) laser

with wavelength λPA = 2πcωPA

to produce the photoassociation reaction; from Eqs. (1)

and (6), neglecting the kinetic energy terms in Eq. (5), we consider two kinds of

transitions, according to the hyperfine level in the initial state,

for the dark SPOT experiments. The rovibrational level of a long-range molecu-

lar state u,g —labeled here in Hund’s case c notation—is thus populated. PA is

achieved by continuously illuminating the cold Cs atoms with the beam (λPA

852 or 894 nm) of a Ti:sapphire laser (“Coherent 899” ring laser) pumped by an

argon-ion laser, red-detuned from the 6s( f = 4) → 6 p3/2 ( f ′ = 5) atomic transi-

tion (11732.183 cm−1 (Avila et al., 1986), or from the 6s( f = 4) → 6 p1/2 ( f ′ = 3)

atomic transition (11178.07 cm−1). The frequency scale is calibrated using a Fabry–

Perot interferometer, and the absorption lines of iodine (Gerstenkorn et al., 1982).

The maximum absolute uncertainty is estimated to be ±150 MHz, mainly due

84 F. Masnou-Seeuws and P. Pillet

to the uncertainties on the position of the iodine lines. Thanks to the Perot–Fabry

interferometer, which has a free spectral range of 750 MHz, the local uncertainty

is reduced to about ±10 MHz. The maximum available power of the laser beam

is 650 mW. We approximate the intensity by a Gaussian profile, exp(−2ρ 2 /w02 ),

with w0 = 300 ± 50 μm, leading to a maximum intensity of 450 W cm−2 for the

PA laser.

The Orsay experiment uses two kinds of detection schemes for the photoassociation

process and the formation of molecules in the ground or lower triplet state.

r As in many photoassociation experiments (see Stwalley and Wang, 1999, and

references therein), trap-loss analysis is performed recording the fluorescence

yield from the trap, collected by a photodiode. The variations of the signal

are interpreted as decrease of the number of atoms in the trap due both

to dissociation of PA molecules into a pair of atoms that escape the trap

[Eq. (46)] and possibly to the formation of cold ground-state molecules.

r Second, Cs+ 2 ions are detected through a time-of-flight mass spectrometer,

after photoionization of the translationally cold Cs2 molecules. The photons

are provided by a pulsed dye laser (λ2 ∼ 716 nm, 7-ns duration) pumped by

the second harmonic of a Nd-YAG laser; the ionization is a REMPI process,

using as intermediate step the vibrational levels of an electronic molecular

state correlated to the (6s + 5d3/2,5/2 dissociation limits (Fioretti et al., 1998)

(see Fig. 9). There is a window of a few hundred wavenumbers around the

wavelength λI ≈ 716 nm and another window is observed for λ′I ≈ 554 nm,

corresponding to the REMPI process via vibrational levels correlated to

6s + 7s. The time-of-flight scheme discriminates atomic and molecular ions.

The sensitivity of ion detection for probing the formation of molecules is a

key point of these experiments. The upper vibrational levels of the ground

state cannot be detected in the present scheme (Dion et al., 2001), due to the

selection rule forbidding (6s → 5d) atomic transitions. Estimations show

that presently the detection efficiency is only about 5%.

C. PHOTOASSOCIATION SPECTRA

The fluorescence and the Cs+ 2 ion spectra are recorded as a function of the PA

laser frequency. A summary of the Orsay data is shown in Fig. 10 with typical

spectra obtained by using a MOT atomic sample. The origin of the energy scale is

fixed at the 6s1/2 , f = 4 → 6 p3/2 , f ′ = 5 atomic transition, which corresponds to

an energy of 11732.183 cm−1 above the 6s1/2 , f = 4 + 6s1/2 , f = 4 asymptote.

FORMATION OF ULTRACOLD MOLECULES 85

FIG. 9. The detection scheme in the Orsay experiment. It is a two-photon resonant process (REMPI)

via vibrational levels in the (2) 3 g potential curve correlated to the Cs (6s) + Cs (5d) dissociation

limit. Ultracold molecules can be detected both in the ground X 1 g+ and metastable a 3u+ states.

For detunings smaller than 0.1 cm−1, the MOT is destroyed by the PA laser. The

fluorescence and the Cs+

2 ion spectra are quite different.

while the trap-loss spectrum stops beyond 40 cm−1 and of only 40 cm−1 for

the trap-loss.

r Second, the density of resonance lines in the trap-loss spectrum is much more

important.

1. Trap-Loss Spectrum

In the fluorescence spectrum, recorded as a function of the detuning of the

photoassociation laser, we observe dips interpreted as vibrational progressions.

The presence of a dip corresponds either to a photoassociation reaction followed

by dissociation,

(51)

where it is assumed that E c′ is large enough so that the two atoms live the trap,

or to a photoassociation reaction followed by spontaneous emission into a bound

86 F. Masnou-Seeuws and P. Pillet

FIG. 10. Cs+ 2 ion signal (lower signal) and trap fluorescence yield (upper signal) versus detuning of

the PA. In the inset, details of the rotational structure of the 0−

g v = 10 level is shown. The dashed line

indicates the correspondance of vibrational levels of the 0− g state on both spectra. Notice the different

scales for the axis. The spectra are the results of a large number of scans.

FORMATION OF ULTRACOLD MOLECULES 87

+

(6s + 6s; v0 , J )] + h(ω0 + δ3 ).

(52)

0−g (6s 1/2 + 6 p 3/2 ) states. About 80 lines for each vibrational progression are well

resolved in the range 2–45 cm−1. The 1u state does not seem to be present in the

fluorescence spectrum. The reason is that the dissociation of the photoassociated

1u molecules after spontaneous emission do not produce “hot” enough atoms to

escape the trap: in other words, E c′ is smaller than the trap depth. In the energy

range of about 5 cm−1, the observed linewidths are mostly due to the hyperfine

structure and in qualitative agreement with the computed ones of about 6, 1.5, 0.6,

and 6 GHz for the 1g , 0+ −

u , 0g , and 1u, respectively (Fioretti et al., 1998).

To verify the identification of the lines, a fit can be performed with the semi-

classical Le Roy–Bernstein law already discussed in Section II.B,

1/6 −1/3

D i − E vi = A3 (v D − v) C3i

, (53)

where the dissociation limit D i , the constant A3, and quantum number v D have

been defined in Eqs. (24) and (25). The relation between C3i and C3 = 6s|dz |6 p
2

is given by Julienne and Vigué (1991):

√

5 7+2

C31 = C3 (0+

u) = C3 C32 = C3 (1g ) = C3 (54)

3 3

The fit allows us to identify the excited electronic states, and to obtain val-

ues for their dissociation energies and for the constant C3 (see the reviews

by Weiner et al., 1999; Stwalley and Wang, 1999). In the cesium experi-

ments not reviewed in the quoted papers the following values are obtained:

D fit (1g ) = −3 ± 1 GHz, v fitD (1g ) = 212.9 ± 0.5 (this refers to numerotation v = 0

for δ1 = −44.141 cm−1 ) and C3fit (1g ) = 15.72 ± 0.05 atomic units for the 1g state

fit

and D fit (0+ +

u ) = −7.8 ± 1.1 GHz, v D (0u ) = 214.0 ± 1 (this refers to numerota-

tion v = 0 for δ1 = −44.336 cm , and C3fit (0+

−1

u ) = 16.1 ± 0.4 atomic units for

the 0+ u state. C 3 coefficients are in 4% and 9% agreement with the calculated values

[C3 (1g ) = 16.22 a.u., C3 (0+ u ) = 17.46 a.u.], Marinescu and Dalgarno (1995). But

the atomic lifetime τ deduced from the fitted C3 coefficients,

3

hǫ0 λ

τ= (55)

2e2 6s|dz |6 p
2 2π

88 F. Masnou-Seeuws and P. Pillet

(Volz and Schomoranzer, 1996). Notice that the fits are performed in a range

of detuning (larger than 4 cm−1) where the hyperfine structure is not expected to

perturb noticeably the −C3 /R 3 behavior. The uncertainty of the fitting coefficients

illustrates their variation according to the number of lines included in the fit. Some

more accurate fit, including the higher multipolar expansion in the asymptotic

part of the potential, should give more accurate prediction. Other effects, such as

predissociation of 0+ u (Kokoouline et al., 2000b) should also be considered. As

mentioned by Fioretti et al. (1998), the Le Roy–Bernstein approach does not work

very well for fitting the asymptotic potential of 0− g , due to its particular double-

well character, with smooth variation of the potential in the bump zone between the

inner and outer wells. Similar conclusions were obtained by Fioretti et al. (2001)

for the equivalent double-well in the Rb2 case.

2. Ion Spectrum

The ion signal is more selective than the trap-loss one, only the vibrational pro-

+

gressions of the 0−

g and 1u states being present in the Cs2 spectrum. The detection

−

procedure can be optimized, for either 0g or 1u, by adjusting the wavelength of

the pulsed laser used for the photoionization. The detection is here sensitive up to

a detuning range of 80 cm−1 for the PA laser.

+

Cs2 0−g Pure Long-Range State. The Cs2 ion spectrum exhibits 133 well-

resolved structures assigned as the vibrational progression in the outer well of

the 0−

g ( p3/2) state, starting at v = 0. The rotational structure, shown for v = 10

in the inset of Fig. 10, is resolved up to J = 8 for most of the vibrational

levels below v = 74.1 The energies of the spectral lines have been fitted with a

Rydberg–Klein–Rees (RKR) and near-dissociation expansion (NDE) approach,

giving, for the outer well, an effective potential curve with a 77.94 ± 0.01 cm−1

depth and an equilibrium distance Re = 23.36 ± 0.10a0 (Fioretti et al., 1999).

This provides good knowledge for the vibrational wavefunctions and for the inner

and outer turning points of the classical vibrational motion up to v = 74. The 0− g

long-range well filled potential of various alkali dimers has been characterized

by photoassociation spectroscopy: the experimental values for the spectroscopic

constants have been determined for Na2 (Ratliff et al., 1994), where hyperfine

structure has to be included, for K2 (Wang et al., 1996), who obtain a well depth

and position De = 6.49 cm−1 , Re = 14.63a0 , Rb2 (Cline et al., 1994), where

1

The large number of observed rotational levels is due to a cooperative effect between the cooling

laser and the PA laser (Fioretti et al., 1999). In fact, if the cooling is switched off during the PA phase,

at a temperature T ≤ 30 μK, only s-waves have to be considered in the experiment with excitation of

only J = 0 and J = 2 rotational levels. At T ≃ 200 μK s-, p-, and d-waves are essentially present and

the excitation of rotational state up to J = 4 is possible.

FORMATION OF ULTRACOLD MOLECULES 89

De = 28.295 cm−1 . As discussed in Section II.A, the well depth De = 77.94 cm−1

found by Fioretti et al. (1999) is much larger for Cs2.

Two giant structures at detunings δ1 = 2.14 cm−1 and δ2 = 6.15 cm−1 will be

described in Section V.C. We remark that the variation of level spacing follows

approximately the 5/6 scaling law as a function of detuning: in the vicinity of a

1-cm−1 detuning, the level spacing is ∼0.6 cm−1, whereas close to hδ L = 10 cm−1

the level spacing increases up to ∼3.6 cm−1, in qualitative agreement with the

6.8 factor predicted by the scaling law. More refined verification should take into

account the derivative of the level energy, and the variation of the C3i coefficient

as a function of distance Rvi . The modulation of the line intensities, due to the

nodal structure of the ground-state wavefunction, described in Section II.E, is

clearly visible. It has been noticed (see, for instance, Côté et al., 1995; Tiesinga

et al., 1996) that this modulation can be used for the determination of collision

parameters such as scattering lengths. Up to six of the eight visible nodes could

be used by Drag et al. (2000b) to fit the ground triplet scattering length aT.

The slow variation of the maximum intensity as a function of detuning can be

qualitatively explained by a compensation beween the −7/6 variation of the pho-

toassociation rate and the 5/6 variation of the bound–bound transition probability

provided we may prove that the molecular ion signal is a signature of the presence

of molecules in the a 3 u+ lower triplet state.

Cs2 1u Pure Long-Range State. The large structures in the Cs+ 2 ion spectrum in

the range (3–6 cm−1) are assigned to the 1u state. The Cs+ 2 ion spectra, recorded as

a function of the PA laser frequency for the MOT and the dark SPOT devices, are

shown in Fig. 11. The MOT spectrum exhibits both the 0− g and the 1u vibrational

progressions, while the 0− g progression is dominated by the 1u one in the dark

SPOT spectrum. The observed intensities corresponding to the same vibrational

levels are different for the MOT and the dark SPOT experiments, which is not

surprising because the two spectra correspond to two different initial states of the

collisional process [see Eqs. (50) and (51)], with two free atoms in either the f = 4

or f = 3 state. For the 1u state, the intensities corresponding to the dark SPOT

are on average 10 times larger. One notices also that the vibrational level, v = 0,

appears in the dark SPOT spectrum but not in the MOT spectrum. Conversely,

higher vibrational levels, up to v = 12, are observed in the MOT spectrum.

Figure 12 shows the well-resolved structures of the vibrational levels v = 0,

1, and 2 of the 1u state. The spectrum does not exhibit any simple progression,

neither hyperfine nor rotational. To interpret these complex structures, Comparat

et al. (2000) have performed systematic asymptotic calculations including both

hyperfine structure and molecular rotation, for all the electronic states involved in

1u photoassociation. They had not to introduce exchange energy in the calculations

since this quantity remains small at the position (about 25a0) of the inner wall of

90 F. Masnou-Seeuws and P. Pillet

FIG. 11. Cs+2 ion signal versus detuning of the photoassociation laser in the dark SPOT device

(a) and in the MOT (b). For the dark SPOT spectrum, the frequencies are shifted by 18.384 GHz.

FIG. 12. Zoom of Cs+ 2 ion signal versus detuning of the PA laser in the dark SPOT device, for the

1u vibrational levels v = 0 (a), v = 1 (b), and v = 2 (c).

FORMATION OF ULTRACOLD MOLECULES 91

FIG. 13. Structure of the v = 0 line of the 1u vibrational progression, compared in mirror with the

calculated intensities. The frequency of the first observable line is arbitrarily taken as zero.

the 1u potentials. The complete calculation of the positions and the intensities of

the lines, in which the only adjustable parameters are the initial populations of the

different partial waves (from s to g, here), agree very well with the experiment

(see Fig. 13). More than the 0− g state, the 1u state can really be labeled as a pure

long-range state, corresponding to a pair of atoms, the cohesion of which is given

by the electrostatic long-range multipole interaction (Stwalley et al., 1978).

Up to now, although we have identified selective population of the 0− g ( p3/2 ) and

lu ( p3/2) excited states in the ion spectrum, we have not yet proved the presence of

ground-state ultracold molecules. Indeed, the molecular ions could be produced

directly by photoionization of an excited state. To rule out this explanation, we

analyze the Cs+ 2 ion signal by considering the following temporal sequence: first

the PA laser beam is applied during 15 ms, then the ionizing laser pulse (7-ns

width) is delayed compared to the switching on of the PA laser. We observe that

the Cs+ 2 ion signal decreases with a characteristic time of the order of 10 ms

(see Fig. 14). This time is five orders of magnitude larger than the radiative lifetime

of any singly excited molecular state with electric-dipole allowed transition to the

ground state. Indeed, this characteristic time is of the order of the time during

92 F. Masnou-Seeuws and P. Pillet

FIG. 14. Time evolution of the Cs+ 2 ion signal when the photoassociation laser is turned on and off.

The exponential decrease corresponds to a characteristic time Td ≈ 10 ms, much larger than the radiative

lifetime of the photoassociated molecules (Tsp ≈ 30 ns). This result demonstrates that the photoion-

ization scheme is indeed starting from long-lived ultracold molecules in the ground singlet or triplet

state. The decrease of the signal is due to the fact that those molecules are falling down from the trap.

which molecules can move significantly out of the trap because of gravity. This

result clearly indicates that ions are not produced by direct photoionization of PA

excited molecules, but indeed by photoionization of the ground-state molecules.

Why, in contrast with earlier discussion, has reaction (52) a favorable branching

ratio in the case of two particular symmetries? This can be explained by the very

particular shape of the outer well for the two relevant potential curves, discussed in

Section II.A. Due to the smooth ∼R−3 behavior of the inner branch of the well, the

vibrational motion is gradually slowed, and there is a non-negligible probability

of presence at the inner turning point, as is manifested in Fig. 15, to be compared

with Fig. 4 representing an “ordinary” vibrational wavefunction. The efficiency

of the mechanism for the formation of cold molecules comes from the existence

of a Condon point at intermediate distance, as shown schematically in Fig. 16. In

all cases photoassociation occurs at long-range distance. The dissociation reaction

(51) can always take place (i), but spontaneous emission may also occur at a short

enough interatomic distance [case reaction (ii) or (iii)], forming cold ground-state

(ii) or lower triplet-state (iii) molecules. This is due to the particular vibrational

motion in the 0− g or 1u external wells, where a long time delay is spent at both

the outer and inner turning points. In contrast, in the case of the 1g or 0+ u state,

the reflection on the inner repulsive wall is very rapid, so that the vibration of the

excited molecule keeps the two atoms at large interatomic distance most of the time.

Therefore, the formation of translationally cold molecules is attributed to the

particular shape of some of the external potential wells in the heavy-alkali dimers,

which offer at the same time an efficient photoassociation rate and a reasonable

branching ratio for spontaneous emission toward the ground state. A confirmation

of this mechanism has been demonstrated in rubidium by Gabbanini et al. (2000).

FORMATION OF ULTRACOLD MOLECULES 93

g (6s + 6 p3/2 ) potential of Cs2, for a

binding energy v = 6 cm−1 .

E. TRANSLATIONAL TEMPERATURE

These cold ground-state Cs2 molecules are not trapped by the MOT and can be

detected below the trap zone (Fioretti et al., 1998; Comparat et al., 1999). The

spatial analysis of the ballistic expansion of the falling molecular cloud yields

FIG. 16. Mechanism for the formation of ultracold molecules, from the relevant potential curves of

Cs2. The photoassociation process occurs at large distance. Line (i) represents spontaneous emission

toward continuum states, with dissociation of the molecule; lines (ii) and (iii) represent spontaneous

emission toward bound states, with formation of stable cold molecules.

94 F. Masnou-Seeuws and P. Pillet

FIG. 17. Temperature measurement through time of flight: recordings (i–iv) correspond to the

temporal analyzis of Cs+

2 ion signal at the MOT position (i), and at 0.95 mm (ii), 1.90 mm (iii), and

2.85 mm (iv) below the MOT position.

a measure of the temperature of the molecular cloud. The ground-state cold Cs2

molecules are photoionized into Cs+ 2 ions, using here the dye laser focused on spot

of 300 μm diameter. Two kinds of measurements of the molecular temperature

have been performed. The first one consists of photoassociating the cold atomic

sample during a time of 3 ms. The fall of the molecular could is then temporally

analyzed at different distances below the atomic trap. Figure 17 shows a time-of-

flight analysis at different positions below the cold-atom trap. The theoretical fit

of the experimental data gives access to the temperature, and also allows one to

determine precisely the height of the fall. The other measurement of the tempera-

ture of the molecules relies on the analysis of the ballistic expansion for different

heights, using the dye laser beam focussed on a spot with the same 300 μm

diameter. Figure 18 depicts the spatial analysis of the falling molecular cloud. A

model proposed by A. Lambrecht et al. (1996), taking into account the formation

and the fall of the cold molecules, allows one to derive the molecular temperature

from the data. A temperature as low as 20+15

−5 μK has been determined. The atomic

temperature, measured similarly by photoionizing the cold Cs atoms into Cs+ ions,

lies in the range 20–30 μK, showing no difference with the molecular temperature.

F. PHOTOASSOCIATION RATE

The measurement of the rate of formation of cold molecules could be obtained

directly by using the Cs+

2 ion signal. Unfortunately, this signal is difficult to analyze,

because the efficiency of the photoionization process is badly calibrated, probably

not better than 10%. Taking into account the ion recollection and the detector

efficiency, the global efficiency of the detection does not exceed a few percent.

FORMATION OF ULTRACOLD MOLECULES 95

FIG. 18. Temperature measurement through ballistic expansion: recordings correspond to the spatial

analyzis of Cs+

2 ion signal at the MOT position (i), and at 1.90 mm (ii) and 3.80 mm (iii) below the

MOT position.

This first estimation leads to a cold molecule formation rate of 0.1 per atom and

per second in the conditions of a MOT. For a precise determination, it is preferable

first to measure the PA rate by using the trap-loss signal and then to deduce the

formation rate by using the calculated branching ratio between bound–bound and

bound–free transitions of the photoassociated molecules.

Drag et al. (2000a) have so performed accurate trap-loss measurements for the

two states 0+ −

u and 0g (6s + 6 p3/2 ). To determine the experimental PA rates, they

have considered the dynamic trap equation (Hoffmann et al., 1994) expressing the

balance between the loading rate and the various loss rates, for a total number

of trapped atoms Nat and a density nat,

d Nat

= − γ Nat − (β + βPA ) n 2at (r ) d 3r, (56)

dt vol

where γ is the loss rate due to background gas collisions, β is the loss rate due

to binary collisions among the trapped atoms, and βPA is the loss rate resulting

from PA among the trapped atoms.2 In the steady-state regime, the total number

of trapped atoms is measured with or without the PA laser. In the former case,

the resonance line intensity for the considered rovibrational level is recorded.

Considering the Gaussian distribution of the atomic density and assuming that it

is not too much affected by PA, determine the ratio

NPA γ + βn at

≃ . (57)

Nat γ + (β + βPA )n at

2

The coefficient βPA is weighted by a factor corresponding to the partial overlap between the cold

atomic volume and the laser beam (see Fig. 8c).

96 F. Masnou-Seeuws and P. Pillet

Knowing the quantity γ + βn at , one may deduce the parameter βPA . The lat-

ter quantity corresponds to the inverse of the characteristic loading time of the

MOT, which has been measured as τ ≃ 735 ms, with the experimental con-

ditions of the MOT n at = 1011 cm−3, T = 140 μK. They obtain in this way

−2 −1

n at βPA (0+

u , 200 W cm ) = 3.5 ± 0.5 s , for the level corresponding to a res-

−1

onance line located at 14.35 cm below the dissociation limit and for a PA laser

intensity of 200 W cm−2. They have measured the rate n at βPA (0− −2

g , 55 W cm ) =

2.45 ± 0.6 s−1 for the v = 77, J = 2 level and for a PA laser intensity of 55 W

cm−2 . More generally, in the Orsay experiments, for all the states observed in the

energy range 5–10 cm−1 below both dissociation limits 6s + 6 p3/2 and 6s + 6 p1/2 ,

PA rates measured through trap losses have values ranging roughly between 1 and

5 s−1 (Drag et al., 2000a). The determination of the formation rate of cold molecules

is discussed below in 5 V.B.

The molecules formed through PA are indeed translationally cold. But after sponta-

neous emission the cold molecular sample is found in a statistical mixture of a few

rovibrational levels, determined by the Franck–Condon factors. To obtain ground-

state molecules that are cold in all degrees of freedom (translation, vibration, and

rotation) is still a challenge. Putting all the molecules in the same rovibrational

level is a necessary step to get a molecular sample useful for further experiments.

Stimulated Raman PA, where the emission on a given bound–bound transition is

stimulated (see the scheme of the relevant levels in Fig. 19), offers such a possibil-

ity (Bohn and Julienne, 1996; Vardi et al., 1997). Stimulated Raman PA has been

used in a Rb condensate, where molecules should be formed, but up to now no

direct evidence of their presence could be produced (Wynar et al., 2000). It has

been demonstrated for the cesium atom, by using a MOT device. (Laburthe-Tolra

et al., 2001)

The principle of the experiment consists, for a pair of colliding cold Cs atoms

prepared in the hyperfine level f = 3, in having a Raman two-photon transition to

form directly a ground-state X 1 g+ molecule in a well-defined final rovibrational

level v, J . In fact, as the ground-state vibrational levels reached are located energy-

wise in the vicinity of the dissociation limit, the gerade/ungerade symmetry is

broken due to hyperfine coupling, and the electronic ground state corresponds

to a superposition of singlet and triplet characters (Comparat et al., 2000). The

intermediate level, labeled 1 in Fig. 19, is a hyperfine-rotational component of the

vibrational level v = 0 or 1 of the 1u state, which will be specified later. The first

laser, labeled L1, is detuned by a value on either the red side or the blue side of

the resonance of the PA transition,

FORMATION OF ULTRACOLD MOLECULES 97

FIG. 19. Relevant energy levels of the stimulated Raman PA transition, from a continuum of states

α of the two colliding atoms to a final bound level (2) of the ground state molecule. and δ correspond

to the detunings of lasers L1 and L2 compared to the PA transition α → 1 and to the stimulated Raman

PA transition α → 2. The laser L2 can also produce one-photon PA.

so that no PA due to the laser L1 can be observed. We scan the frequency of the

laser L2 to make resonant (δ = 0) the Raman transition toward the final ground-state

level, labeled 2. One has

continuously illuminated by the laser beam L2, a pulsed laser beam L1 (τ = 2.5 ms;

this time is chosen to avoid a too significant decreasing of the atomic density). The

laser beam L1 is provided by the Ti:sapphire laser with an available intensity in the

MOT zone of 450 W cm−2. A Pockels cell is used for switching. The laser beam

L2 is provided by a DBR diode laser (SDL 5712-H1, 100 mW) with a maximum

available intensity of 50 W cm−2.

Figure 20a shows the PA Cs+ 2 ion spectrum obtained by applying only the

laser L2 with an intensity of 30 W cm−2, and by scanning its frequency around

the resonance corresponding to one-photon excitation (process shown by the

dot-dashed arrow in Fig. 19) of the vibrational level v = 1 of the 1u (6s + 6 p3/2 )

state. One has

→ Cs2∗ [1u (6s + 6 p3/2 ); v = 1]. (61)

98 F. Masnou-Seeuws and P. Pillet

FIG. 20. (a) PA spectrum of the 1u v = 1 level, by scanning laser L2. (b) Same as (a) but in the

presence of laser L1. (c) Stimulated Raman PA resonance. The inset analyzes the Raman character of

resonance (c).

The maximum of detected ions is here of the order of 100 per shot. The dashed

arrow shows on this spectrum a very well resolved and isolated line. This resonance

corresponds to the excitation of the hyperfine level, labeled 1, with a total angular

momentum F = 7, and with a wave function close to

It is the total nuclear spin, and MI and are respectively the projections of It

and of the total electronic angular momentum, Jt = 1, on the molecular axis. The

spectrum in Fig. 20b was obtained under the same conditions as previously, but

by applying at the same time the Ti:sapphire laser (L1). The frequency of laser

L1 (see the dotted line of Fig. 20) is now detuned by −20 MHz compared to the

resonance 1. The Cs+ 2 ion signal is 1.5% of the ion signal with laser L1 tuned

to resonance 1, which means less than 10 ions per shot. This number is com-

parable to the Cs+ 2 ion background due to the presence of cold molecules in the

MOT even without applying any PA laser (Fioretti et al., 1998; Gabbanini et al.,

2000; Takekoshi et al., 1998). Nevertheless, the presence of the laser L1 perturbs

the L2 spectrum. This perturbation is not fully understood, but it probably cor-

responds to further excitation of the 1u molecules toward highly excited states.

Another characteristic of spectrum (b) compared to (a) is the appearance of new

broad structures as shown by the full-line arrow. Reducing the intensity of the

laser L2 down to only 2 W cm−2 produces no more direct PA signal due to L2, but

maintains the existence of the extra structures which appear now as very narrow

resonances (see Fig. 20c) corresponding to the formation of cold Cs2 molecules

FORMATION OF ULTRACOLD MOLECULES 99

in a well-defined level of the ground state through stimulated Raman PA. The

Raman character of the resonance has been tested by red- and then blue-detuning

by quantities ≃ ±40-MHz laser L1 from resonance 1. The inset in Fig. 20

shows the shift of the resonance by a quantity ∼80 MHz. It has been verified

experimentally that the position of the line is fixed by the frequency difference of

the two lasers. The stimulated Raman PA signal of Fig. 20c corresponds to about

50–100 detected ions, meaning a number of cold molecules of about 1000, within

a factor of 3. The difficulty of a precise estimation of the cold-molecule num-

ber comes from the rough estimation for photoionization efficiency (Drag et al.,

2000a; Dion et al., 2001).

H. OTHER EXPERIMENTS

The case of the cesium atom is very demonstrative for the use of PA for the for-

mation of cold molecules. We have already demonstrated the possibility to ob-

tain cold molecules in the ground state or the lowest triplet state at temperature

in the range 20–200 μK with a formation rate typically varying between 0.05

and 0.2 molecule per atom and per second for the experimental conditions in

Orsay (atomic temperature 20–200 μK, density 4 × 1010 atoms/cm3). For 50 mil-

lion trapped atoms, 2.5 to 10 million ultracold molecules are formed per second.

We can also form state-selected molecules with similar characteristics by using

the stimulated Raman photoassociation. Is it possible to extend the case of the

cesium atom and dimer to other species? The answer is not obvious, because the

efficiency of the mechanisms is based on the particular double-well shape in the

0−g and 1u (6s + 6 p3/2 ) potentials curves, creating a Condon point at intermediate

distance. Among other alkali atoms, only the rubidium present a similar char-

acteristic for the 0−g (5s + 5 p3/2 ) state. The formation of cold Rb2 molecules in

the lowest triplet state has been demonstrated by Gabbanini et al. (2000). The

formation of translationally cold K2 molecules in their singlet ground state has

been demonstated via photoassociation of the A1 u+ (4s + 4 p3/2 ) state (Nikolov

et al., 1999). Here the molecular configuration does not correspond to a long-range

outer well. The branching ratio for bound–bound transitions is not as important

as for the cesium and rubidium experiments, and the rate for the formation of

cold molecules is only 1000 per second for the considered experimental condi-

tions. This number is nevertheless more important as compared to most of PA

experiments, and is due to an accidentally non-negligible Franck–Condon fac-

tor for a given bound–bound transition. More complex schemes of formation of

cold molecules have been proposed, with PA of highly excited molecular states

(Band and Julienne, 1995; Bohn and Julienne, 1996). An efficient production of

K2 molecules has indeed been achieved by using a two-step excitation scheme.

In this case, highly excited molecules radiate toward various vibrational levels of

the X ground state, with a rate comparable to the one achieved for cesium atom

100 F. Masnou-Seeuws and P. Pillet

(Nikolov et al., 2000). The supplementary difficulty is the use of a second pho-

toassociation laser but the method is a general one.

The conclusion of this section is that the formation of cold molecules via PA

can certainly be extended to any species which can be previously laser-cooled.

The demonstration of novel mechanisms for the formation of ultracold molecules

make this route very promising. However, a last difficulty in making these cold

molecular samples useful for applications is to be able to trap them. The trapping

of cold molecules with a CO2 laser quasi-electrostatic trap has been demonstrated

(Takekoshi et al., 1998,1999). These trapped cold molecules are not formed via PA,

but are those naturally present in the MOT trap. This result should be extended to

molecules formed directly by photoassociation in such a trap. Unpublished results

obtained in Orsay have demonstrated the possibility of trapping cold molecules

in the lowest triplet state by using a quadrupolar magnetic trap. Trap devices

for molecules should show rapid developments in the next years. They should

allow one to accumulate up to 104–106 ultracold molecules in a 10- to 100-μK

temperature range, eventually in a well-defined rovibrational level of the ground

state (or the lowest triplet state) if stimulated Raman PA is used. The PA experiments

using a condensate should also show interesting developments (Wynar et al., 2000).

We did not develop in this review this kind of very exciting results, which should

lead to the possibility of observing a molecular condensate or a molecule laser.

The coherence of the Raman process is here a key point making the conception of

these experiments a little different.

The theoretical treatment of cold-atom collisions has stimulated many new devel-

opments, which can be found, for instance, in the review of Weiner et al. (1999). In

the present review we shall focus on progress that was specially motivated by the

research on ultracold molecules, insisting upon the necessary accuracy in estima-

tion of Franck–Condon overlap as described in Section II.D. The specific technical

problems are:

of the vibrational motion in regions where the potential is very weak. Accurate

description of the nuclear motion requires methods capable of describing

both the short-range region, where chemical potentials are acting, and the

long-range region.

r In addition, the dynamics is very sensitive to the accuracy in the electronic

potential curves, and the requirement is well beyond the present accuracy of

FORMATION OF ULTRACOLD MOLECULES 101

data should be revisited for the present problem.

FOR PHOTOASSOCIATED MOLECULES

We have seen above that the estimation of the photoassociation rate is controlled

by the matrix element of the electronic dipole moment between the continuum

wavefunction in the ground state and the bound vibrational wavefunction in the

excited state [see Eqs. (34) and (35)]. Numerical accuracy in the estimation of this

quantity is a key for a good comparison between theory and experiment. Although

well-established techniques have long been developed in molecular physics for

that purpose, the problem of cold molecules presents some specific difficulties.

We give in Fig. 8 an example of a typical vibrational wavefunction for a level close

to the dissociation limit of the Cs21g( p3/2). The local de Broglie wavelength λ(R),

in atomic units, is with h = 1, is

2π

λ(R) = , (63)

2μ[V∞ − V (R)]

and depends on the value of the potential V (R), which varies by several orders

of magnitude from the short-range region to the asymptotic region. It is clearly

visible in Fig. 8 that the local de Broglie wavelength is varying from a few tens of

a0 in the outer region to a value less than 1a0 in the inner region, i.e., by more than

one order of magnitude from the short-range region to the long-range region. The

numerical or analytical methods should be adapted to this situation, and the use

of a radial coordinate adapted to the local de Broglie wavelength is the key for all

developments.

Grid numerical methods using fast Fourier transform have proved to be very effi-

cient for quantum molecular dynamics (Kosloff, 1988, 1996). Wavefunctions and

operators are represented on grids in both the momentum and coordinate spaces.

It is convenient to use constant grid steps, which is linked to the minimum value

of the local de Broglie wavelength. For calculations of the vibrational levels of

a diatomic molecule, a Fourier grid method, originally proposed by Marston and

Balint-Kurti (1989) and by Colbert and Miller (1992), was further developed by

Monnerville and Robbe (1994), Dulieu and Julienne (1995), and Dulieu et al.

(1997), and proved to be very successful. The wavefunction may be represented

by its values at a set of N equally spaced radial distances between the two distances

102 F. Masnou-Seeuws and P. Pillet

R1 and R1 + N × s = R1 + L,

N /2

ψ(Ri ) = ak gk (Ri )(i, j = 1, N ), (64)

k=(−N /2+1)

L

Ri = R1 + (i − 1)s , s = (65)

N

functions at the grid points through the relation

N /2

gk (Ri )gk (R j ) = δ(Ri − R j ) (i, j = 1, N ). (66)

k=(−N /2+1)

(67)

outgoing plane waves, with wavelength varying from 2s to L, choosing

1 2kπ R

gk (R) = √ exp −i , (68)

N L

N N

kǫ − + 1, . (69)

2 2

N

1 i2kπ R j

ak = √ ϕ(R j ) exp , (70)

N k=1 L

spaced grid points in the momentum space, pk = 2kπ/L. The two representations

are connected by Fourier transform, the basis set in momentum representation,

conjugated to the coordinate representation basis set defined in Eq. (68), being

1

f j ( p) = √ exp(−i p R j ). (71)

N

π π

pN = N = , (72)

L s

FORMATION OF ULTRACOLD MOLECULES 103

where s is the constant grid step defined in Eq. (65). It is then straightforward to

represent all operators by N × N matrices either in coordinate or in momentum

representation. The radial Schrödinger equation,

involves two operators. The matrix V(R) is diagonal in the coordinate representa-

tion, while the kinetic energy operator T( p) is diagonal in the momentum repre-

sentation and can be easily evaluated. After Fourier transform, it is written in the

coordinate representation as

π2 N2 + 2

Tii = , (74)

μL 2 6

π2 1

Ti j = (−1)i− j 2 2

. (75)

μL sin [(i − j)π/N ]

The computation effort involved in the diagonalization procedure scales

as N3. The choice of the constant step, and therefore of N, is linked to the maxi-

mum momentum in the physical problem or to the minimum value of the local de

Broglie wavelength,

λ(Re ) π

s ≤ = , (76)

2 2μ(V∞ − VRe )

obtained at the equilibrium distance Re where the potential is minimum. In the ex-

ample of the v = 332 excited wavefunction in the 1g potential presented in Fig. 8,

the calculations would require at least diagonalization of a 8200 × 8200 matrix.

However, the grid step is unnecessarily small in the long-range region. Fattal et al.

(1996) and Kosloff (1996) have proposed a mapping procedure in order to optimize

the use of phase space in grid methods, with application to Coulomb potentials. This

mapping procedure has been generalized to the present problem by Kokoouline

et al. (1999), who have introduced a variable grid step adapted to the local

de Broglie wavelength,

π λ(R)

s(R) = = , (77)

2μ[V∞ − V (R)] 2

the physical potential for all internuclear distances, for instance, the analytical

104 F. Masnou-Seeuws and P. Pillet

π

senv (R) = . (78)

2μ[V∞ − Venv (R)]

The number of grid points is markedly reduced when the step size is defined by

Eq. (77) and the same accuracy can be obtained by diagonalization of a 564 × 564

matrix. This matrix is obtained by defining a grid in a new coordinate x such that the

variable step in R corresponds to a constant step in x. We therefore use a Jacobian

J (x) such that

d R = J (x) d x, (79)

λ(R)

J (x) = . (80)

λ(Re )

d2 J′ d 5 (J ′ )2 1 J ′′

1 1

− + + V + − + φ(x) = Eφ(x),

2μJ 2 d x 2 μJ 3 d x 2μ 4 J4 2 J3

(81)

7 (J ′ )2 1 J ′′

1

V (x) = V (x) + − . (83)

2μ 4 J4 2 J3

( )

π2 1 1 1

Ti, j = (−1)i− j 2 2 2

+ 2 , (84)

2μL sin [(i − j)π/N ] Ji Jj

if i = j, while

π2 N2 + 2 1

Ti,i = . (85)

μL 2 6 Ji2

FORMATION OF ULTRACOLD MOLECULES 105

Therefore calculations are performed in the working grid using the coordinate x

with a constant grid step. The vibrational energies are then obtained by diagonal-

ization of the Hamiltonian in the new representation. The wavefunctions have to

be transformed making use of Eqs. (83) and (81) to obtain results in the physical

grid R. If the potential V (R) is given as a set of numerical values, the procedure

is straightforward. However, as the derivation involves first and second derivatives

of the Jacobian J (x), care must be taken that such derivatives are well defined. In

many applications, the potentials are obtained by matching short-range potentials

computed by ab initio method to long-range asymptotic expansion, and interpola-

tion procedures have to be carried out carefully. An alternative procedure consists

of considering an enveloping analytical potential for the definition of the new

variable x. Choosing, for instance, a potential Venv (R) = −Cn /R n with n = 2, the

change of variable in Eq. (81) becomes analytical, and for a grid starting at distance

Rin we may define an adaptative coordinate through the formula

√ ( )

2 2μCn 1 1

x= − (n−2)/2 . (86)

π (n − 2) R (n−2)/2 R

in

As discussed by Kokoouline et al. (1999), this procedure is less efficient than

the preceding one, making use of the real potential, as far as optimization of the

phase space is considered, but the calculations now use analytic formulas, which

may save computing time. Finally, we should note that the wavefunction defined

at grid points can be interpolated without further loss of accuracy by use of the

Fourier expansion,

N

π

ψ(q) = ψ(q j ) sinc (q − q j ) , (87)

j=i

q

ate point, q is a grid step, and we have defined the function sinc(z) = [sin(z)/z].

In Fig. 21 we display the wave function, computed with sinc interpolation at a

large number (Ninterp = 10,000) of q values, for the (v = 332) vibrational level of

Cs2(1g). Comparison with linear interpolation clearly illustrates the good quality

of the second interpolation. Of course, we have checked the accuracy of the inter-

polated wavefunctions by comparing to standard methods. The wavefunction in

the adaptative coordinate x is displayed in Fig. 22, illustrating the regularity of the

oscillations.

The grid points can be used for the Fourier expansion of the wavefunction,

yielding useful properties in numerical quadrature. It is possible to use MFGR

representation with the same grid for the ground- and excited-state wavefunctions

106 F. Masnou-Seeuws and P. Pillet

FIG. 21. (Upper) The v = 332 vibrational wavefunction for the 1g (6s + 6 p3/2 ) potential of Cs2,

with binding energy v = 0.0419 cm−1 , Computed at the grid points defined with the mapping of

the Eq. (82). Here, the grid extends up to 500a0, and contains N = 564 points. (Lower) Interpolation

procedure. The wave function ψ(R), R = R j , is interpolated as Eq. (89) in text.

so that excellent accuracy can be obtained for an overlap integral of the two func-

tions; this seems one of the main advantages of a grid method. It can be easily

generalized to double-well potentials, as will be discussed later in the example

of tunneling effect, and to calculations with several channels, including predisso-

ciation problems where coupling between bound and continuum levels has to be

considered (Kokoouline et al., 2000b). In the method described above, all vibra-

tional levels are computed up to a maximum energy. It may be convenient to limit

the calculations to a given energy range by use of filtering techniques: in particular,

in the vicinity of a dissociation limit, there is a large density of levels. A mapping

procedure is introduced by Tiesinga et al. (1998) in a filtering method making use

of Green-function operators to resolve the hyperfine structure for the levels close

to the Na(3s ) + Na(3p ) asymptote.

The choice of the number of grid points is presently determined by optimization

of the use of the classical phase space (Fattal et al., 1996; Kokoouline et al., 1999).

FIG. 22. Interpolated wavefunction in the x variable, adapted to the local de Broglie wavelength.

The graph shows only the part corresponding to large R. Comparing with Fig. 21, one can appreciate

the regularity of the oscillations in the mapped wavefunction.

FORMATION OF ULTRACOLD MOLECULES 107

For low-energy scattering, or for levels close to the dissociation limit, the extension

of the wavefunction in the classically forbidden region increases, and this effect

has been up to now empirically addressed by an increase of the number N of points.

A proper treatment of the classically forbidden region, with a priori calculation

of the number of points necessary to represent the classically forbidden region,

still has to be implemented; it should benefit from the expertise developed by the

groups working on analytical representation of the wavefunction (Boisseau et al.,

2000b).

Many groups working in the field of cold collisions and long-range molecules

have used the well-known Numerov–Cooley algorithm (Cooley, 1971, and ref-

erences therein), both for bound and continuum wavefunctions, often using the

Blatt criterion (Blatt, 1967) to choose the step length by minimizing local trunca-

tion error. For bound and predissociated levels, the Cooley–Cashion–Zare routine

SCHR has been regularly modified and improved by the group at the University

of Waterloo (Canada), and the present version (Le Roy, 2000) includes variable

steps. We should also mention introduction of a variable step in Numerov integra-

tion by Côté and Jamieson (1995), the step size being divided by a factor of 2 each

time the local wavenumber becomes smaller than a given parameter. Comparison

with the grid methods described above still has to be carefully done, in order to

check accuracy and efficiency. The present situation is such that potentials data

being usually given for a limited number of internuclear distances, with a large

mesh size, results depend on the method chosen for interpolation. An accurate

comparison should consider a potential in an analytical form, or implement the

same interpolation procedure.

In the case of a two-channel problem, with both bound and continuum solutions,

a recent paper by Rawitscher et al. (1999) compares various approaches to compute

scattering wavefunctions and extract the scattering length and effective range. For

two coupled potentials of Lennard–Jones type, with an exponential coupling term,

equivalent results are obtained by

r A noniterative eigenchannel variant of the R-matrix method (Aymar et al.,

1996),

r A Gordon method (Gordon, 1969) as modified by Mies (1973).

The third one is easier to implement but necessitates a much larger number of

points. In contrast, an improved Numerov method is shown to yield much poorer

accuracy. The authors conclude with the necessity of performing similar compar-

ison under more complex conditions.

108 F. Masnou-Seeuws and P. Pillet

3. Analytical Treatment

Analytical solutions of the radial Schrödinger equation have been proposed by

many authors, mainly in the framework of the JWKB approximation. At zero

scattering energy, Gribakin and Flanbaum (1993), in a paper which is considered

one of the main references in cold collisions, obtained an analytical expression of

the scattering length by transforming the radial equation into a Bessel equation.

We should note that the change of variable is

√

2 2μCn 1

x= (n−2)/2

, (88)

(n − 2) h R

similar to the change of variable introduced in Eq. (86) at the limit R0 → ∞, Rin

with h = 1. Future work might benefit from this analogy. For the description of

bound levels, many authors have worked within the framework of the semiclassical

approximation defined above. Close to the dissociation limit, where the part of the

wavefunction that extends into the nonclassical region becomes important, correc-

tions to the first-order JWKB approximation have been implemented. Friedrich and

Trost (1996a,b), Trost and Friedrich (1997); Trost et al. (1998) introduce a Maslov

index modifying the /4 reflexion phase at the outer turning point, and changing

the Bohr–Sommerfeld quantization condition in Eq. (15). Another approach, by

Boisseau et al. (1998, 2000b), considers second-order JWKB terms and numerical

corrections to the quantization condition. The two derivations give the same re-

sults. Gao (2000) has discussed in detail the breakdown of Bohr’s correspondence

principle. As discussed above, numerical calculations can also be implemented in

the region where the first-order semiclassical treatment fails.

AND ELECTRONIC DIPOLE TRANSITION MOMENTS

One reason why the comparison between theory and experiment happened to be

relatively easy in the case of K2, Rb2 and Cs2 dimers is that accurate potentials

were available at both short and long internuclear distances. We should cite, for

short distances, the pseudo-potential ab initio calculations of Meyer’s group (Spies,

1989) for Cs2, of Foucrault et al. (1992) for Rb2 and Cs2, of Magnier and Millié

(1996) for K2 and NaK, and of Magnier et al. (1993) for Na2. In addition, a lot

of spectroscopic information is available, very accurate potentials being fitted to

experimental spectra: let us cite, among many other examples, the recent fit of

ground-state potential for the Rb2 molecule by Seto et al. (2000), where 99.8%

of the potential well can be deduced from a fit to 12,148 transition frequencies

in a high-resolution A–X emission spectrum. For implementation of the detection

scheme using absorption to an intermediate state, knowledge of excited potential

curves and transition dipole moments is essential. In that case, the information

FORMATION OF ULTRACOLD MOLECULES 109

iments with dense alkali vapors in a heat pipe (Pichler et al., 1983; Beuc et al.,

1982; Veza et al., 1998), has also proved very helpful. In contrast, recent results on

photoassociation of calcium (Zinner et al., 2000) have not been fully interpreted

due to the lack of theoretical information.

The matching between short-range ab initio calculations and long-range expan-

sion (Marinescu and Dalgarno, 1995, 1996; Derevianko et al., 1999), and refer-

ences herein. Next must be performed (see Fig. 3). Discussion on the accuracy of

long-range coefficients is beyond the scope of the present chapter, and can be found

in various papers (Stivalley and Wang, 1999). The computed values either agree

with experiment or must be modified by a few percentage. This can be verified

on the values given in §C1 for the C3 coefficients. Finally, it should be wise to

remember from the two previous sections that when potentials are computed on a

set of internuclear distances, the mesh size should be sufficiently small to avoid

loss of accuracy due to the interpolation procedure.

and Theory: Formation Rates

As examples of comparison between theory and experiment, we shall discuss

the determination of photoassociation rates and absolute number of ultracold Cs2

molecules obtained in Orsay, as well as the demonstration of a tunneling effect

from analysis of the spectra.

A. PHOTOASSOCIATION RATES

Using for Cs2 the set of potentials obtained by matching the ab initio calculations of

Meyer’s group (Spies, 1989) to asymptotic curves using the long-range coefficients

of Marinescu and Dalgarno (1995), the photoassociation rates were computed with

the numerical methods developed above and compared to experiment (Drag et al.,

2000a).

In Fig. 23 we display the quantities RPA in s−1 (number of photoassociated

molecules formed per second divided by the total number of atoms) defined in Eq.

(36) and κPA = RPA /n at /(I /hωPA ), defined per photon and per unit density, for

photoassociation into a vibrational level of the double-well 0− g (6s + 6 p3/2 ) curve,

and of the long-range attractive 0−g (6s + 6 p1/2 ) curve. The detuning δ L of the laser

is relative to the D2 and D1 resonance lines, respectively, and is varied on the entire

range covered by the 0− g (6s + 6 p3/2 ) external well. The photoassociation rate

displays minima at detunings such that Rvi corresponds to the nodes in the ground-

state wavefunction, as discussed in Section II.E. The intensity of the maxima

decreases as a function of the detuning of the laser: for photoassociation into a

110 F. Masnou-Seeuws and P. Pillet

FIG. 23. Computed cesium photoassociation rates, RPA (in s−1) and κPA (in cm−5), for molecu-

lar states of 0−

g symmetry correlated to 6s + 6 p3/2 (closed circles) and to 6s + 6 p1/2 (open circles).

Experimental parameters are chosen: T = 140 μK, n at = 1011 cm−3 , I = 55 W/cm2 . We notice a mod-

ulation in the rates due to the nodal structure of the initial continuum state wavefunction (see text). The

dot-dashed lines indicate the PA rate given with the approximate formula (55) in the work of Pillet et

al. (1997), approximating the continuum wavefunction by its asymptotic sine behavior.

−7/6

behavior predicted

by the simple model described in Section II.F. We should notice the importance

of the decrease, the rate varying by two orders of magnitude when the detuning

increases from 1 cm−1 to 50 cm−1.

−6

In contrast, as the 0− g ( p1/2 ) potential curve displays R asymptotic behavior

i

(due to cancellation of the C3 coefficient), the scaling law is different (Wang and

Stwalley, 1998) and the decrease is slower. We notice that, despite the C6 long-range

behavior, the corresponding PA rates are not negligible, being roughly one order

of magnitude smaller than in the previous case. This result is of some interest for

future studies of PA in heteronuclear species, which also present R−6 long-range

behavior (Wang and Stwalley, 1998).

An interesting result of the calculations is the importance of the correct de-

termination of the correct ground-state wavefunction. In Fig. 23, we also display

rates computed with a E (R) continuum wavefunction approximated by a free-

wave sine function: the corresponding curve is overestimated by more than one

order of magnitude, and of course does not represent the minima at the nodes of

the real E (R) function. This confirms that the bottleneck in the photoassociation

process is the amplitude of the initial wavefunction, demonstrating the advantage

of performing experiments at small detunings.

Precise comparison between experiment and theory has been presented by

Drag et al. (2000a) for photoassociation into the vibrational levels of the 0− g and

−1

0+u (6s + 6 p 3/2 ) curves, at detunings 6.92 and 14.35 cm , respectively, below the

FORMATION OF ULTRACOLD MOLECULES 111

6s( f = 4) + 6 p3/2 ( f ′ = 5) limit, for which atomic loss rates have been measured.

The main source of uncertainty lies in the experimental parameters (atomic density

nat, temperature T, laser intensity I ) which have to be introduced in the calculations.

The measured atom loss rates are determined under experimental conditions with

nat = 1011 cm−3, T = 140 ± 20 μK, I = 55 W/cm2 for 0− g and I = 200 W/cm

2

+ 2

for 0u . The calculations use T = 140 μK and I = 55 W/cm in both cases.

For the 0− +

g and 0u photoassociation rates, the theoretical values are, respectively,

of 6.6 and 5.8 molecules s−1, in good agreement with the experimental values

of 2.4 and 3.5 molecules s−1 (assuming simply that the atom loss rate is twice

the PA rate). Both calculated and experimental rates lie within the margin of 1–5

excited molecules formed per second and per atom, for a total number of atoms

Nat = 5 × 107, estimated within a factor of 2. This means that all atoms in a MOT

could be transformed into excited molecules in a time less than 1 s.

The next step is the estimation of the percentage of the photoassociated molecules

that may be stabilized into long-lived molecules. The rate equation for the number

Nexc(v, J ) (or simply Nexc) of molecules photoassociated in a rovibrational state

(v, J) by the laser can be written as

d

Nexc = RPA Nat − Ŵexc Nexc , (89)

dt

where Ŵexc is the spontaneous emission probability of level (v, J ) and Nat is the

number of atoms in the trap at time t. Provided that RPA ≪ Ŵexc ≈ Ŵ, the number

of atoms Nat is assumed to be constant, as the trap loading time is longer (∼700 ms)

than all other characteristic times in the problem. In such conditions, the system

−1

reaches within a time Ŵexc a stationary state with a constant number N̄ exc of excited

molecules,

RPA

N̄ exc = Nat (0). (90)

Ŵexc

The number of long-lived ultracold molecules Ncold (t) produced at time t by spon-

taneous emission can be estimated as

(t) bound

Ncold = Ŵexc N̄ exc t, (91)

bound

where Ŵexc is the spontaneous emission probability of the excited level v toward

all levels v ′′ of the molecular ground and lower triplet states. One can write,

112 F. Masnou-Seeuws and P. Pillet

FIG. 24. (a) Probability of populating vibrational levels of the ultracold molecules in the a 3 u+ state,

after spontaneous decay from the photoassociated levels lying in the external well of the 0− g (6s + 6 p3/2 )

state (black circles) or in the 0−

g (6s + 6 p1/2 ) curve. (b) Number of ultracold molecules formed in the

a 3 u+ state after photoassociation and spontaneous emission.

t bound RPA

Ncold = Ŵexc Nat (0)t. (92)

Ŵexc

Neglecting the R dependence of the transition dipole moment, the ratio between

bound–bound and total spontaneous emission probabilities in Eq. (93) can be

approximated by

bound

Ŵexc

= |v0 |v
|2 = S(v → g), (93)

Ŵexc v0

where the sum runs over all bound vibrational levels v0 of the molecular ground

or (metastable triplet) state g. Selection rules for the PA rate are the same as for

spontaneous emission. We present in Fig. 24 the S(v → g) sums computed for the

3 +

transitions 0−

g (6s + 6 p3/2 ; v, J = 0) → a u over detunings covering the entire

−

energy range of the 0g external well. In the calculations of Drag et al. (2000a), the

FORMATION OF ULTRACOLD MOLECULES 113

vibrational levels v0 in the ground triplet state have been considered up to a binding

energy of 0.4 cm−1, the upper ones being not detected in the experiment. As ex-

pected, the variation of S as a function of detuning is opposite to the variation of the

5/6

PA rate, due to the v dependence of the normalization factor Nv2 [see Eq. (29)].

The decay occurs by vertical transition at intermediate distance, and the probabil-

ity increases at large detuning due to the increase of the normalization factor. The

lowest levels of the 0− g (6s + 6 p3/2 ) long-range well are shown to decay almost com-

pletely into bound levels. For comparison we have also reported the bound–bound

branching ratios for the 0− g (6s + 6 p1/2 ; v, J = 0) state, where, due to a different

scaling law, the dependence on detuning is much weaker. At all detunings, the weak-

3 +

ness of S[0− g (6s + 6 p1/2 ; v, J = 0) → a u ] population transfer, due to the lack

of a Condon point at intermediate distance, confirms the difficulty of identifying

the vibrational levels of the 0− g (6s + 6 p1/2 ) state in the ion spectra, since the prob-

ability of forming metastable a 3 u+ molecules is small.

When the photoassociation rate is multiplied by the probability of decay into a

bound level, we obtain the curves given in Fig. 24b, where the number of ultracold

molecules formed per second in the trap is given as a function of detuning. The

minima correspond to the zeros in the photoassociation rate at nodes of the ground-

state wavefunction. The maxima display a slow decrease as a function of detuning,

−7/6

due to the balance between the v decrease of the photoassociation rate and

5/6

the v increase of the probability of spontaneous decay into a bound level.

This result explains an interesting feature in the Cs+ 2 photoassociation spec-

trum for the 0− g (Fioretti et al., 1999) double-well long-range state (see Fig. 10),

where, apart from the intensity minima already discussed in previous works (Côté

et al., 1995; Fioretti et al., 1998; Drag et al., 2000b), the average number of

detected molecular ions is roughly constant over the entire energy range investi-

gated (∼80 cm−1). Assuming comparable ionization efficiency for all vibrational

levels v0 , this would indicate that the formation rate of ultracold molecules for

this particular double-well state in Cs2 is nearly independent of the choice of v

in the photoassociation process. This has been predicted in Section II from the

balance between the two scaling laws: a level v close to the dissociation limit of

the excited state will be populated efficiently (due to favorable Franck–Condon

factors at large distances), but will poorly emit toward bound levels v0 of the

lowest electronic states, due to the low probability amplitude in the vibrational

i

wavefunction φv,J (R) at intermediate distance. The situation is exactly oppo-

site for the lowest levels v of the excited state: the very large branching ratio

for decay to bound levels in the 3 u+ curve is associated with a very small PA

rate, such that the calculations predict no formation of cold molecules, as is

effectively observed (Fioretti et al., 1999). The conclusion is that, in order to

get a large rate for ultracold-molecule formation, one needs a good compromise

between the PA rate and the branching ratio for the bound–bound spontaneous

emission.

114 F. Masnou-Seeuws and P. Pillet

Except at very low detunings, the calculations yield an average theoretical rate

oscillating beween 0.1 and 0 triplet ultracold molecules per second and per atom.

This number is in reasonable agreement with the rates obtained directly from

trap-loss measurements, where a number of 0.05 to 0.2 molecule per second and

per atoms seems a good estimate (Drag, 2000a). It is also compatible with the

values deduced from the measured number of ions: a global rate for the formation

of cold molecules is between 2 × 105 and 106 molecules per second, in a trap

containing Nat ≈ 50 million atoms.

Concerning other alkali atoms, only rubidium offers a similar outer well in its

0−g (5s + 5 p3/2 ) state. The number of cold Rb2 molecules is found to be smaller

than for Cs2 as the outer well is located at a greater distance, reducing by a factor of

3 the bound–bound branching ratio (Fioretti et al., 2001). The number of cold K2

molecules obtained by Nikolov et al. (1999) by one-step photoassociation is only

about 1000 molecules per second, due to the absence of a similar external well.

In contrast, the two-step scheme of Nikolov et al. (2000) produces 105 molecules

per second and per vibrational level, or 106 molecules per second when summing

over all vibrational levels, which is the same formation rate as in the cesium case.

The time delay to transform half the atoms into molecules is therefore estimated

to be less than 1 minute in all the present experiments, showing that the process is

indeed very efficient.

An even better efficiency might be obtained if the photoassociation process was

simultaneously populating a large number of levels, using, for instance, broad-

band pulsed laser excitation: at low detunings, the small value of the amplitude of

the vibrational wavefunction of each individual level in the excited state would be

compensated by the number of levels, increasing the flux toward the ground state.

C. TUNNELING EFFECT

Another scheme for formation of ultracold molecules in low vibrational levels

of the a 3 u+ Cs2 state was identified in the photoassociation spectrum of Fioretti

et al. (1999), manifested by detection of a large number of molecular ions. In

the experimental ion spectrum displayed in Fig. 10, we can see two “giant” lines,

corresponding to binding energies 1 = 2.14 cm−1 , 2 = 6.153 cm−1 relative to

the 6s + 6 p3/2 dissociation limit. Details of the observed spectrum are given in

Fig. 25. The “giant” structures have a well-resolved rotational structure in con-

trast to the neighboring lines identified as vibrational levels of the outer well of

the 0−g (6s + 6 p3/2 ) potential curve. Vatasescu et al. (2000) have analyzed the data

showing that the rotational constants Bv1 = 137 MHz and Bv2 = 189 MHz associ-

ated to vibrational levels of the two structures are typical of motion in the inner

well. This can be deduced from the definition of the rotational constant as Bv =

h 2 /2μR 2
with μ = 121135.83 a.u., giving an estimate of the mean value of the

internuclear distance R̄ = h/(2μBv )−1/2 . For G1 and G2 structures, respectively,

FORMATION OF ULTRACOLD MOLECULES 115

FIG. 25. Details of the photoassociation spectra in the region of the (a) G1 and (b) G2 structures,

with their J labeling. Such structures are embedded in the vibrational progression of regular levels

(a) v = 102–105, (b) v = 79–81 with unresolved rotational structure. The rotational constants of the

giant structures G1 and G2 are obtained from the slopes of the lower curves giving the variation of the

binding energy as a function of J (J + 1).

this yields R̄ 1 ≈ 14a0 and R̄ 2 ≈ 12a0 , whereas the hump in the double-

well potential is located at a distance Rb ≈ 15a0 . The spectroscopy results could

be reproduced by theoretical calculations, and we show in Fig. 26 an example

of a vibrational wavefunction with tunneling. In the inner region, coupling with

vibrational motion in the potential curve 0− g (6s + 5d) has to be considered, so

that the function displays several Condon points favorable to spontaneous decay

toward low-lying bound levels of the a 3u+ Cs2 state. The large intensity of the ion

signal at the detunings corresponding to 1 and 2 binding energies could be an

116 F. Masnou-Seeuws and P. Pillet

FIG. 26. Tunneling effect: vibrational wavefunction extending both in the outer well of the 0− g (6s +

6 p 2 p3/2 ) potential curve of Cs2 and in the inner well. In the inner region, coupling with the 0−

g (6s + 5d)

vibrational series has to be considered.

indication of a good efficiency for this scheme, but better analysis of the detection

efficiency as a function of the vibrational number v 0 of the final molecule has to

be performed.

Due to the complexity of potential curves in a given molecule, it seems that many

new schemes can be proposed owing to collaboration between theory and exper-

iment. If we stay within the present scheme of photoassociation with continuous

laser light, it seems wise to perform photoassociation at large internuclear dis-

tances and to look for situations where the vibrational motion is gradually stopped

at intermediate distance, providing opportunity to populate bound levels in the

ground-state potential curve by spontaneous emission. Besides potential barriers

with a gentle slope, which are not easily encountered, a more general mechanism is

offered by resonant coupling. In many situations, the excited-state potential curve

i is dynamically coupled to another one, i′ . Looking for resonances beweeen the

two vibrational series, one can transfer population from a level v i of the first series

to a level v i ′ of the other one. Dion et al. (2001) have recently shown that a large

number of ground-state Cs2 molecules are indeed observed in experiments where

a loosely bound level v i of the 0+ u (6s + 6 p1/2 ) curve is populated by photoassoci-

ation, and the population transferred to a level v i ′ of the narrower 0+u (6s + 6 p3/2 )

FORMATION OF ULTRACOLD MOLECULES 117

curve, which is has good Franck–Condon overlap with bound levels of the ground

state. This scheme is summarized in Fig. 27. Two-step photoassociation, with

transfer of population to bound levels of the lowest Na2 1u Rydberg excited

curve, has been discussed by Band and Julienne (1995), while Almazor et al.

(1999) proposed to populate a double-well curve in the Na2 (6) 1 g+ excited state.

Another possibility consists of considering photoassociation with pulsed lasers,

and trying to control the formation of molecules. This has been discussed by

several authors (Vardi et al., 1997; Vala et al., 2001), but no absolute rate has been

given up to now in the condition of the experiments. Vala et al. (2001) propose to

enhance the photoassociation rate by use of chirped pulses. In the work of Vardi

et al., two nanosecond pulses are used, one for photoassociation, another one for

population transfer by induced emission to a precise bound level v0 in the ground

excited curve. The estimation of 6 × 10−6 molecules formed per pulse and per atom

indicates that this process is much less efficient that the present schemes using CW

lasers. Half the atoms could be converted to molecules in ∼25 mn, whereas the CW

experiments predict times of the order of a few seconds. However, all long-lived

molecules would be produced in the same vibrational level v0 , which is not the

case in the present experimental schemes with CW lasers. The main advantage

of pulsed excitation is that a large number of levels can be photoassociated at the

same time, increasing at low detunings the flux to bound levels of the ground state

as discussed in Section V.B. We have shown in Section II.B that at low binding

energies all photoassociated vibrational levels have a similar wave function at short

and intermediate internuclear distance, and therefore similar spontaneous emission

probabilities toward levels of the ground state.

VII. Conclusion

While direct laser cooling of molecules is not at present a promising technique,

this chapter shows that an efficient way of making ultracold molecules is to start

from a sample laser-cooled atoms, and to implement a two-step process: first, a

photoassociation reaction creates, out of two atoms, a bound molecule in an ex-

cited electronic state, and second, this short-lived molecule decays by spontaneous

emission to bound levels of the ground electronic state (or lower triplet state).

The photoassociation process, first suggested by Thorsheim et al. (1987), uses

laser light slightly red-detuned with respect to an atomic resonance line, and can

be understood as a vertical (Franck–Condon) transition at large distance Rvi be-

tween a continuum level (two colliding atoms) and a bound level v in an ex-

cited electronic curve i of the molecule. The photoassociated molecule can be

viewed as a pair of distant atoms, weakly bound by dipole–dipole interaction: for

loosely bound vibrational levels, the two atoms are most of the time moving in the

asymptotic region of weak interaction, the outer classical turning point Rvi being a

118 F. Masnou-Seeuws and P. Pillet

electron, the binding energy of a level being linked to its vibrational number by the

Le Roy–Berstein formula generalizing the Rydberg formula. Scaling laws are

found, showing that the photoassociation process is favored at very small detun-

ings, corresponding to vertical transitions at large distance. In such conditions, the

photoassociated molecule usually decays back into a pair of ground-state atoms.

Indeed, the ground-state potential curve, with asymptotic R−6 behavior, is much

narrower than the excited curve, and bound levels can be efficiently populated by

spontaneous emission only when the nuclei are at short or intermediate distance. In

most cases, the vibrational motion of the photoassociated molecule is such that the

amount of time spent in the short-range region is too small, making the branching

ratio between stabilization and dissociation negligible.

However, experiments by Fioretti et al. (1998, 1999), using photoassociation

in a cesium sample and detection of molecular ions by a REMPI scheme, have

demonstrated for some symmetries (0− g , 1u ) of the photoassociated molecule, an

efficient mechanism for population of bound levels in the ground (or lower-triplet)-

state potential curve. This can be explained by the double-well structure of the 0− g

and 1u curves, where a barrier at intermediate distance is gently slowing down

the vibrational motion, increasing the time spent at distances where spontaneous

emission can efficiently populate a bound level of a ground (or lower triplet) state

of the molecule. A similar mechanism exists for rubidium, and was demonstrated

by Gabbanini et al. (2000). At present, in a cesium trap containing 50 million atoms,

at a density nat = 1011 cm−3 and temperature T = 140 μK, using continuous pho-

toassociation lasers with intensity ≤1 kW/cm2, it is possible to create from 105 to

106 molecules per second, that is, to transform 10% of the atoms into molecules in

a time of a few seconds. Similar results were obtained by Nikolov et al. (2000) for

K2 using another mechanism where the photoassociated molecule is excited by a

second laser to a Rydberg state which decays by spontaneous emission to bound

levels of the ground electronic state. Presently, we should note that only a few

molecules (∼5%) thus formed are detected. The sensitivity of the REMPI detec-

tion should be improved, and the ionization step optimized, in collaboration with

molecular spectroscopy groups. Once most molecules are detected, the formation

of ultracold molecules will appear as a very strong effect.

The interpretation of experiments and design of new schemes relies on close

collaboration between theory and experiment. New theoretical methods have been

developed to treat ultracold molecules, and their comparison with more traditional

methods has to be implemented. There is good agreement between measured pho-

toassociation rates and theoretical calculations performed in the framework of a

perturbative treatment. An important result is the rapid decrease of the photo-

association rate as a function of detuning, interpreted by scaling laws, and by

the behavior of the initial continuum-state wavefunction, which has a reduced

probability amplitude at small internuclear distances. The photoassociation pro-

cess is thus more efficient at low detuning. In contrast, the branching ratio for

FORMATION OF ULTRACOLD MOLECULES 119

at low detuning, due to a smaller amplitude of the vibrational wavefunctions of

the photoassociated molecule in the intermediate distance region where to bound

levels is possible. Present experiments have to choose a compromise between the

efficiency of the photoassociation step and the efficiency of the stabilization step.

Some new schemes that rely on tunneling effect, resonant coupling, or two-step

excitation were also shown to be efficient, and must be further explored.

The photoassociation rate is presently estimated in the framework of a per-

turbative treatment, and comparison with more sophisticated theoretical studies

using time-dependent formalism still has to be implemented. Photoassociation us-

ing pulsed lasers has been little explored as yet experimentally (Boesten et al.,

1996, 1998) but seems a promising route. The conclusions of the present chap-

ter concern photoassociation rates for population of individual vibrational levels.

Different conclusions would be drawn if broad-band excitation was used in the

photoassociation process, as the population of a large number of levels, with sim-

ilar wavefunctions in the short- and intermediate-distance region, would increase

the efficiency of the stabilization process. The discussion of pulsed laser experi-

ments connects the subject of cold-molecule formation to the general problem of

coherent control.

Current results could be extended to all homonuclear systems provided a dense

enough sample can be obtained. Formation of heteronuclear molecules, although

presenting smaller photoassociation rates, would have the advantage of making

the trapping process easy with a dipole trap. Indeed, at present the molecules stay

for roughly 10 s inside the trap, and then fall down. The next important step is to

trap them. A CO2 laser, used in the experiments of Takekoshi et al. (1998, 1999)

seems promissing. Magnetic trapping has been used for triplet molecules, and first

demonstration has been achieved recently in Orsay. The rotational temperature of

the ultracold molecules is low, but they are formed in a large number of vibra-

tional levels, so a Raman scheme to lower the vibrational temperature should be

implemented. Coherent control techniques (Bartana et al., 1993, 1997) also offer

interesting possibilities.

The optimization of the rate of molecule formation should be searched for in

an increase of the atomic density rather than an increase of the laser intensity,

which may lead to saturation or reexcitation. We are reaching there the field of

atomic condensates, which is beyond the scope of the present review but offers

very interesting opportunities: the choice between two routes toward molecular

condensates, either creating molecules within an atomic condensate (Wynar et al.,

2000) or bringing a dense ensemble of ultracold molecules to conditions where

Bose condensation can take place, is an interesting perspective. The molecule laser

would be an important application.

Other applications lie in threshold laws for collisions (atom–molecule, Rydberg

atom–molecule, molecule–molecule collisions), very little explored at present

(Forrey et al., 1998, 1999a,b), on the formation of more complex species (trimers

120 F. Masnou-Seeuws and P. Pillet

small clusters). Ultracold molecular sources would be ideal for molecular inter-

ferometry experiments (Bordé et al., 1994; Chapman et al., 1995; Lisdaf et al.,

2000). In short, a new research field is open.

VIII. Acknowledgments

This review relies on work done within the team Molécules et atomes froids in

Laboratoire Aimé Cotton, so we are very indebted to Ph.D. students Cyril Drag,

Bruno Laburthe Tolra, Salah Boussen, and Nathalie Hoang for experiments, Marie-

Laure Almazor, Viatcheslav Kokoouline, Philippe Pellegrini, Benoit T’Jampens,

and Mihaela Vatasescu for theory, to former or present postdocs Andrea Fioretti,

Wilson de Souza Melo, Ricardo Gutteres, and Claude Dion, and to our young or

senior colleagues Daniel Comparat, Olivier Dulieu, Samuel Guibal, Claude Amiot,

and Anne Crubellier. Special thanks are due to Olivier Dulieu and Claude Dion

for their help in preparing the manuscript and figures. Stimulating collaboration

is gratefully acknowledged with R. Kosloff in Jerusalem, (owing to the Arc en

Ciel-Keshet cooperation program and to invitation of F. M-S by the Fritz Haber

Institute where part of the paper has been written), with E. Tiemann, University of

Hannover, (within the Procope Franco-German cooperation program), and with the

group of W. Stwalley in Storrs, University of Connecticut, (within CNRS-NSF co-

operation). We thank T. F. Gallagher (Virginia), G. Pichler (Zagreb), E. Luc-Koenig

(Orsay), V. N. Ostrovsky (St. Petersburg) for collaboration. Finally, we are grateful

to M. Allegrini, R. Côté, A. Dalgarno, J. Dalibard, C. Gabbanini, Ph. Gould, P.

Lett, J. Pinard, L. Pruvost, C. Salomon, and C. Williams for useful discussions.

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ADVANCES IN ATOMIC, MOLECULAR, AND OPTICAL PHYSICS, VOL. 47

THE ATMOSPHERES OF GIANT

PLANETS AND COMETS: NEEDS

FOR SPECTROSCOPIC AND

COLLISION DATA

YUKIKAZU ITIKAWA

Institute of Space and Astronomical Science, 3-1-1 Yoshinodai, Sagamihara 229-8510,

Japan

Department of Astronomy and Space Science, Kyung Hee University, Suwon, 449-701,

Korea

YONG HA KIM

Department of Astronomy and Space Science, Choong Nam National University, Daejeon,

305-764, Korea

Y. C. MINH

Korea Astronomy Observatory, Hwaam, Yusong, Daejeon, 305-348, Korea

II. Spectroscopy of the Giant Planets:

Needs for Spectroscopic and Collision Data . . . . . . . . . . . . . . . . . . . . . 131

A. Ultraviolet and Visible Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . 132

B. Infrared Spectra. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132

C. Molecular Abundances Inferred From Spectroscopic Observations . . . . 135

D. Aurorae . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139

E. Titan. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143

III. Spectroscopy of Comets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145

A. Ultraviolet and Visible Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . 146

B. Infrared Spectra. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149

C. Radio Spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151

D. Isotopic Abundances. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153

E. Collisional Processes for Cometary Spectra . . . . . . . . . . . . . . . . . . . 154

IV. Spectral Databases and Improvements Needed. . . . . . . . . . . . . . . . . . . . 155

V. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157

VI. Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157

VII. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157

All rights of reproduction in any form reserved.

ISBN 0-12-003847-1/ISSN 1049-250X/01 $35.00

130 Y. Itikawa et al.

I. Introduction

The atmospheres of the giant planets and comets are believed to be least modi-

fied from their original compositions compared with the atmospheres of terrestrial

planets and the tenuous atmospheres of icy satellites in the outer solar system.

Planetary astronomers have been studying possible connections between the con-

stituents of these atmospheres and those of local interstellar clouds. Current theo-

ries on the solar system formation are mainly based on the elemental abundances

derived from the spectra of these planetary atmospheres. Comparisons between the

chemical compositions in these atmospheres and those in local interstellar clouds

should be the starting point to elucidate the chemical evolution of constituents

from interstellar nebulae through the proto-solar nebula to the current planetary

atmospheres.

Spectroscopy is the most powerful means for astronomers to unveil the true

nature of these heavenly bodies. Analyzing the spectra of the planetary objects, as-

tronomers have been able to identify molecules, atoms, radicals, ions, dimers, and

haze particles in the planetary atmospheres, and derive abundances of these con-

stituents. The spectra have also been utilized to derive temperatures and pressures

and to infer detailed radiative and collision processes occurring in the atmospheres

of the planetary objects. Spectroscopic observations of the giant planets and comets

from Earth-based and space-borne observatories during the last three decades have

produced a long list of molecules, radicals, and ions. Analyses of these planetary

spectra have often been hampered by the lack of relevant laboratory spectroscopic

data for the constituents of the atmospheres. The crucial data for the analyses in-

clude line positions, quantum-number designations of the upper and lower states,

and line intensities or transition probabilities. In particular, the identification of

the planetary molecules is only possible with the help of laboratory data on the

line positions. There are still hundreds of unidentified lines in the visible region

of cometary spectra. Many of these lines are suspected to arise from the high-

quantum-number transitions of known species. Consequently, proper laboratory

studies of these molecular bands are urgently needed to identify molecules, and

to analyze the spectra of the atmospheres of comets and the giant planets. Recent

high-resolution spectroscopy in the visible range provides opportunity to separate

isotopic molecular lines from adjacent normal molecular lines. These spectro-

scopic observations of the atmospheric molecules leave a great task not only to

planetary scientists, but to experimentalists and theorists in the field of atomic and

molecular physics.

Historically, laboratory spectroscopic studies for the visible region were inten-

sively carried out several decades ago, and most of the visible spectroscopic data

are only stored in the form of hard copies in the literature. Spectroscopists’ in-

terests have moved to other spectral ranges nowadays, leaving behind insufficient

databases for the identification of the cometary and planetary lines. In the infrared

MOLECULAR EMISSIONS FROM THE ATMOSPHERES 131

region of cometary and planetary spectra, there are also unidentified lines, although

infrared databases have been expanding during the last two decades. Many of the

unidentified infrared lines are speculated to be overtone and combination bands

of molecules already identified, but the relevant spectroscopic information is not

sufficient.

Most of the molecular emissions from the giant planets and comets are caused

by the fluorescence of solar radiation. To analyze the spectra quantitatively, ra-

diative transfer calculations are performed. The fluorescence spectra depend on

the rotational/vibrational states of the fluorescing molecules. Those molecular

states are populated through collisions with atoms, molecules, ions, and electrons.

Even some chemical reactions contribute to the balance of the molecular states.

Thus the analysis of planetary spectra also requires the collision data (i.e., excita-

tion/deexcitation cross sections). It should be noted that those collision processes

are directly responsible for auroral emission and infrared thermal emission or radio

waves from the planetary atmospheres.

In the present chapter, an overview is presented for the emission spectra of the

atmospheres of the giant planets and comets. Emphasis is placed on the recent high-

resolution observations with space probes and ground-based telescopes, including

the detailed studies of the recent bright comets, Hale–Bopp and Hyakutake. One

of the main objectives of the spectral observations is to determine the elemen-

tal abundances of the atmospheres, especially isotopic abundances, which are of

great importance in deducing the origin and evolution of the planetary system.

As mentioned above, spectroscopic and collision data play an essential role in the

analysis of planetary spectra. Many of the necessary data, however, are still lacking

or insufficient. The present chapter specifically reports those data needs.

Needs for Spectroscopic and Collision Data

In this section we present spectra of the atmospheres of the giant planets: Jupiter,

Saturn, Uranus, and Neptune. Sections II.A and II.B summarize observational

results of ultraviolet, visible, and infrared spectra of the planets, and radiative

transfer processes in the atmospheres. Among the information obtained from those

spectra, the most important quantity is the molecular abundance, including isotopic

abundance, which is discussed in Section II.C. Section II.D describes the aurorae

of the giant planets. Auroral emissions are induced by the precipitations of high-

energy electrons, protons, or ions on to the high-altitude atmospheric layers from

the magnetosphere. In Section II.E we present spectra of Titan, the biggest satellite

of Saturn and the only satellite which has a thick atmosphere perhaps retaining

signatures of primordial atmospheric constituents due to least modification by faint

sunlights.

132 Y. Itikawa et al.

In the early 1930s, R. Wildt performed a series of spectroscopic observations

of Jupiter, and identified CH4 and NH3 lines in the visible range (Wildt, 1932).

Almost two decades later, the detection of the most abundant molecule, H2, in

Uranus was achieved by Herzberg (1952), and later in Jupiter by Kiess et al.

(1960) via observations of several lines in the 3 0 band of H2. Voyager 1 and 2

ultraviolet spectrometers observed H2 and H emissions from Jupiter’s polar regions

(Broadfoot et al., 1979). In the ultraviolet region, space-borne investigations were

mostly concentrated on the auroral spectra of polar regions of the Jovian planets,

because the auroral emission is intense compared to airglow emission in general.

Continuum and absorption features of the giant planets in the ultraviolet region

have been studied with the International Ultraviolet Explorer (IUE) since 1978

(e.g., Hunt and Moore, 1984). These observations as well as recent observations

with the Hubble Space Telescope (HST) and the Galileo spacecraft are summarized

in Sect. II.D (Aurorae) in detail. The giant planets passively reflect sunlight in the

visible range, not much showing molecular signatures, but in the infrared their

cool atmospheres emit radiation revealing rich information on their constituents

and thermal characteristics.

B. INFRARED SPECTRA

In the late 1960s and early 1970s, the detections of rotational–vibrational bands

of molecules in infrared became possible because of rapid technological devel-

opment in infrared detector systems, especially Fourier transform multiplexing

spectrometers, of which light-gathering ability was higher than other conventional

spectrometers at that time. Gillett et al. (1969) found that the 8.0–11.5 μm range of

Jupiter is depressed substantially below the computed H2 pressure-induced absorp-

tion continuum. By detecting two Q branches of the v2 NH3 band, they confirmed

that the NH3 is an important opacity source near 10 μm. Ridgway (1974a,b) de-

tected C2H2, C2H6, and PH3 in 10-μm high-resolution spectra of Jupiter obtained

with Fourier transform spectrometer (FTS) on the 4-m telescope at Kitt Peak. The

5-μm atmospheric window also provided an opportunity to detect lines of CO, H2O,

and GeH4. Subsequently, Tokunaga et al. (1981) reported a positive detection of

HCN on Jupiter near 13.5 μm.

During the encounter with Jupiter in 1979, the Infrared Interferometer Spec-

trometer and Radiometer (IRIS), a Fourier transform spectrometer on the Voyager

spacecraft, confirmed hydrocarbon molecules detected in the 1970s from Earth-

based observations. Voyager IRIS data taken from the north polar auroral region of

Jupiter showed several diminutive structures, which were later identified as C2H4,

C3H4, C6H6, and possibly a radical, CH3 (Kim et al., 1985). Recently, Saturn

and Neptune spectra obtained by the Infrared Space Observatory (ISO) show an

MOLECULAR EMISSIONS FROM THE ATMOSPHERES 133

2000). The rotational structures of the v2, v3, and v4 bands of CH3 have been an-

alyzed by chemists (e.g., Spirko and Bunker, 1982; Yamada et al., 1981; Hirota

and Yamada, 1982; references therein). However, CH3 line intensities or Einstein

A coefficients, which are valuable for the derivation of a column abundance of

CH3, are needed for future analyses of the rotational structure of the band. ISO

also detected C3H4 and C4H2 on Saturn; C6H6 on Jupiter and Saturn; CO2 on

Jupiter, Saturn, and Neptune; and H2O on Jupiter, Saturn, Uranus, and Neptune

(e.g., see a summary of the ISO results in Bézard et al., 1999, and references

therein).

Noll et al. (1989, 1990) reported detections of AsH3 in the atmospheres of

Jupiter and Saturn near 5 μm. The possibility of the existence of H2S in Saturn,

Uranus, and Neptune has been proposed by several microwave observations

(Grossman, 1990; de Pater et al., 1991), although the spectral lines of the molecule

were never been unambiguously identified. Eventually, the mass spectrometer on

the Galileo probe detected H2S with a mole fraction of 1 × 10−5 (Niemann et al.,

1996). The mixing ratios of the major constituents of Jupiter’s atmosphere, H2 and

He, have also been determined by the Galileo probe mass spectrometer along with

mixing ratios or upper limits for less abundant molecules including CH4, H2O,

NH3, C2H6, C3H8, C2H4, and H2S, and the inert gases Ne, Ar, Kr, and Xe.

Planetary infrared airglows are due to either fluorescence or thermal emission

of molecules and ions in the upper atmospheres. The existence of global H3+

emission was suspected when the H3+ auroral images of Jupiter were taken at

the Infrared Telescope Facility (IRTF) simultaneously with the spectra of the au-

rora at the Canada-France-Hawaii Telescope (CFHT) (Kim et al., 1991). Ballester

et al. (1994) obtained latitudinal variation of temperatures derived from spatially

resolved H3+ spectra of Jupiter. The global H3+ emissions are found to be de-

creased at the impact site of the comet SL9 fragments on Jupiter, compared with

undisturbed regions at the same latitude (Kim et al., 1996). During the spectral

observations of Jupiter, Trafton et al. (1989) noticed unidentified strong airglow

emission lines near 2.1 μm in addition to the global airglow emissions of H2

quadrupole lines and H3+ lines on November 23, 1988. The unidentified emis-

sions were widespread, but it seems that the emissions might be highly transient

because the emissions were never detected again.

The short-wavelength spectrometer on the ISO successfully detected 3-μm line

emissions from the v3 fundamental and the ν 3+v4−v4 band of CH4 on the disks of

Jupiter and Saturn (Drossart et al., 1999). The similar 3-μm line emissions of CH4

were also detected on Titan from a ground-based observation (Kim et al., 2000; see

the section on Titan). The 3-μm CH4 fluorescence emissions from giant planets and

Titan have not been detected previously from the ground because of strong telluric

absorption, except during an extraordinary event, the collision between comet SL9

and Jupiter in July 1994. From the impact sites of SL9 on Jupiter, a part of the

134 Y. Itikawa et al.

FIG. 1. Strong emission of the ν 3 P branch of CH4 at the A impact site of comet SL9 on Jupiter

(solid line) and a corresponding model spectrum of the P branch (broken line). (From Kim et al., 1996.)

P branch of the CH4 v3 band was detected in emission as shown in Fig. 1 (Kim et al.,

1996; Dinelli et al., 1997). In the future, we expect to detect additional emissions

from other bands of CH4, and from bands of other hydrocarbons, although these

band intensities are expected to be weaker than the CH4 v3 and v3+v4−v4 bands.

We need a database for the Einstein A coefficients of these molecular lines in order

to analyze the hydrocarbon airglows.

For the radiative transfer calculations of thermal infrared radiation in the plan-

etary tropospheres and stratospheres, local thermodynamic equilibrium (LTE) has

been assumed for approximation (e.g., Knacke et al.,1982; Kim et al.,1985). The

LTE approximation greatly simplifies the numerical calculation for the otherwise

complicated radiative transfer processes of thermal infrared radiation in the plan-

etary atmospheres. Above a certain altitude, where atmospheric density becomes

MOLECULAR EMISSIONS FROM THE ATMOSPHERES 135

tenuous, the validity of the LTE breaks down, because the collisional deexcita-

tion rates of molecular vibrational states become less than spontaneous vibrational

transition rates (e.g., Appleby, 1990). However, even above this altitude, ground

rotational states are usually in LTE, since the collisional deexcitation rates of the

ground rotational states are often greater than the spontaneous transition rates

(e.g., Kim et al., 2000). Vibrational states are mostly populated by pumping from

the ground states via solar infrared radiation, not by collisions with other atmo-

spheric species. Since the ground states are the dominant reservoir of the pop-

ulation, excited rovibrational states often follow the rotational population of the

ground states. Therefore, the rotational temperatures derived from emission spec-

tra of infrared airglows and infrared aurorae often represent the ground rotational

temperatures.

SPECTROSCOPIC OBSERVATIONS

Voyager IRIS spectra show very wide smooth continuum absorption in the range

15–40 μm, which is mainly caused by collision-induced absorptions (CIA) of

H2–H2 and H2–He absorptions (Fig. 2). This absorption continuum was utilized

to derive He abundance indirectly with the help of temperature–pressure profiles

derived from Voyager radio occultation experiment (e.g., Gautier et al., 1981).

The He abundances for Uranus and Neptune are 15% and 18% by volume,

FIG. 2. A typical Voyager IRIS spectrum taken from an equatorial region of Jupiter. The smooth

continuum between 15 and 40 μm is caused by pressure-induced H2–H2 and H2–He absorptions. This

continuum has been used to derive a He mixing ratio in Jupiter (e.g., Gautier et al., 1981).

136 Y. Itikawa et al.

respectively, which are consistent with the solar composition of ∼16%. The de-

rived values for Jupiter and Saturn are 13.6% and 3%, respectively, suggesting

that He has been depleted from the upper atmospheres of both planets. The

slight depletion in the atmosphere of Jupiter was confirmed by the in-situ ob-

servations of the Galileo probe (e.g., Niemann et al., 1998). However, a recent

reanalysis of the Voyager measurements by Conrath and Gautier (2000) shows

that the He abundance of Saturn is between 11% and 16%. This new devel-

opment creates a dispute about the current interior models of the giant planets

(e.g., Gautier and Owen, 1989), which are based on the significant He depletion

in Saturn. There have been early attempts to construct temperature-dependent

CIA models (e.g, Trafton, 1967; references therein); and subsequent efforts to

refine the models (e.g., Borysow and Tang, 1993; Zheng and Borysow, 1995;

references therein), which have been compared with laboratory spectra and ap-

plied to the atmospheres of the giant planets. Recent detections of cool brown

dwarfs and Jupiter-size planets orbiting nearby stars demand CIA models for

broad ranges of temperatures and pressures (e.g., Borysow et al., 1997; Trafton,

1998).

Gautier and Owen (1983, 1989) reviewed carbon abundances derived from both

ground and Voyager observations. The C/H ratios compared with the solar value

are 2.3 times for Jupiter, 2.1 times for Saturn, ∼20 times for Uranus, and ∼25

times for Neptune. The carbon and other heavy-element enrichments in Jupiter

were recently confirmed by the measurement of the Galileo probe mass spectrom-

eter. The enrichments seem to increase in the sequence Jupiter, Saturn, Uranus, and

Neptune, and appear to be roughly correlated with the ratio of core mass to total

planet mass (Gautier and Owen, 1989). Gautier and Owen suggested that it may

arise either from efficient upward convection of gases produced from the cores

during the formation of these planets or from the dissolution of infalling plan-

etesimals in the early atmospheres. Recently, based on the Galileo results, Owen

et al. (1999) showed that Ar, Kr, and Xe in Jupiter’s atmosphere are enriched to

the same extent as the other heavy elements.

The detected C3H4 is methyl acetylene. There are two other forms of C3H4:

allene, which has a different order of bonding; and cyclopropene, which has a

simple ring of three carbon atoms surrounded by four hydrogen atoms. Allene

and cyclopropene have not been detected in the giant planets. Benzene (C6H6), a

molecule with a ring of six carbon atoms, was observed in the giant planets, as

mentioned above. On the other hand, cyclopropane (C3H6), another ring molecule,

has not been observed, although propane, C3H8, was detected in the atmospheres of

the giant planets and Titan. It is interesting to investigate why the atmospheres of the

giant planets and Titan do not have observable amounts of allene, cyclopropene,

and cyclopropane. Therefore, good compilation of spectroscopic parameters is

needed for the identification or the derivations of the upper limit abundances of

these molecules.

MOLECULAR EMISSIONS FROM THE ATMOSPHERES 137

Isotopic molecules such as CH3D, HD, and 13CH4 were also detected on Jupiter.

Later, weak lines of 15NH3 were observed nearby strong 14NH3 lines around

10 μm; and H218O was detected through the 5-μm atmospheric window. The

derived 15N and 18O abundances seem to be similar to the solar values, as the

fractionations of heavy species, such as carbon, nitrogen, and sulfur, are less sen-

sitive to chemical reactions in planetary atmospheres, and this is also the case for

cometary isotopic abundances for heavy elements, as discussed in the comet sec-

tion. Gautier and Owen (1983) summarized pre-Galileo D/H values of the giant

planets obtained from Voyager and ground-based observations.

Recently, the mass spectrometer of the Galileo probe accurately measured iso-

tope ratios for D/H, and 3He/4He (Mahaffy et al., 1998), and the D/H ratio is

consistent with Voyager and ground-based data, and recent spectroscopic results

from ISO (e.g., Bézard et al., 1999). The D/H ratio is comparable or a little less

than the value in the local interstellar medium, 1.6 ± 0.12 × 10−5 (Mahaffy et al.,

1998). The D/H ratio of Saturn is similar to that of Jupiter, but the ratios of

Uranus and Neptune are several times higher than those of Jupiter and Saturn (e.g.,

de Bergh et al., 1990). In fact, the values of Uranus and Neptune are equal to or

somewhat less than the D/H ratios of Titan, ∼1.5 × 10−4 (e.g., de Bergh et al.,

1990), P/Halley, ∼3.1 × 10−4 (e.g., Eberhardt et al., 1995), and Earth oceans,

∼1.6 × 10−4. The measured D/H ratios in the atmospheres of the giant planets

suggest that the giant planets may be made from accretions of icy planetesimals,

and the capture of gases from the surrounding proto-solar nebula. The 3He/4He

ratio obtained by the Galileo probe is equal to or a little higher than that found

in meteoritic gases, 1.5 ± 0.3 × 10−4. Niemann et al. (1998) present isotopic ra-

tios measured from the Galileo probe for 13C/12C, 20Ne/22Ne, 38Ar/36Ar, and for

isotopes of Kr and Xe. The derived isotope ratios and heavy-element abundances

are the center of disputes regarding the origin, internal structure, and evolution

of the giant planets (e.g., Owen et al.,1999; Atreya et al., 1999; Manuel et al.,

1998).

Thus far, only CH3D, HD, 13CH4, 15NH3, and H218O have been used to remotely

derive D, 13C, 15N, and 18O abundances from ground spectroscopic observations.

Although the Galileo probe has been successful in the derivation of various iso-

topic abundances, we still need isotopic abundances locked in various molecules,

such as PH3, H2S, etc., in order to investigate the degree of isotopic fractionations

in the atmospheres of the giant planets. The determination of the isotopic fraction-

ation among the molecules will help us in better understanding the chemistry and

convection of the atmospheres. For this purpose we need spectroscopic parame-

ters for the bands of isotopic counterparts of the above molecules, which are not

completely known in the literature.

Weak absorption features in the far-infrared spectra of the Voyager IRIS spectra

of Jupiter and Saturn were attributed to H2–H2 dimers by McKellar (1984) and

Frommhold et al. (1984), after the features were first recognized by Hanel et al.

138 Y. Itikawa et al.

FIG. 3. Spectra of Jupiter at 2.10–2.13 μm compared with a laboratory spectrum of the H2–H2

dimer (bottom). The positions of five S and Q branch lines of H2–H2 and of the S1(1) line of the H2

are indicated. Solar lines are also indicated. (From Kim et al., 1995.)

(1979). Subsequently, Fox and Kim (1984) and Borysow and Frommhold (1986)

attributed features in the far-infrared IRIS spectra of Titan to the H2–N2 dimer. The

2–2.5 μm atmospheric window has been utilized to detect the 2.1-μm features of

H2–H2 dimers from Jupiter (Fig. 3; Kim et al., 1995), Saturn, and Neptune (Fig. 4;

Trafton et al., 1997). The dimer detections through the 2-μm atmospheric window

also suggest the possibility of detecting inert gases such as argon and neon utilizing

sharp spectral structures of H2–Ar and H2–Ne (McKellar, 1995). Since inert gases

do not have strong lines in the visible and infrared ranges, it has been difficult to

derive their abundances in the atmospheres of the giant planets except the in situ

measurements by the Galileo probe (Niemann et al., 1998).

Although extensive laboratory measurements of various dimers have been con-

ducted (e.g., McKellar et al., 1999; McKellar, 1995, 1996; references therein),

theoretical models have rarely been constructed. Even for a simple dimer, H2–H2,

theoretical models have been constructed only for the far-IR S0(0) and S0(1) tran-

sitions by Schaefer and McKellar (1990). The 2-μm v = 1–0 structures, which

can be observed directly with ground-based IR telescopes (e.g., Kim et al., 1995),

have not been modeled. Many spectral lines of various dimers, which have been ob-

served in laboratories by McKellar and his colleagues during the last two decades,

have not been properly designated quantum mechanically.

MOLECULAR EMISSIONS FROM THE ATMOSPHERES 139

FIG. 4. H2–H2 dimer features in near-infrared spectra of Neptune and Saturn (Trafton et al., 1997).

A laboratory absorption spectrum of H2 is shown below Saturn’s spectrum; it includes both the H2 S1(1)

quadrupole line and the associated H2–H2 dimer spectrum, as indicated. A synthetic solar spectrum is

also shown. A schematic spectrum for CH4 is shown near the top for comparison, and the propagated

error spectra for the Neptune and Saturn spectra are shown at the bottom.

D. AURORAE

Auroral particle (electrons, protons, or other ions) precipitation produces electro-

magnetic waves from X ray through visible light to radio range. Jupiter’s strong

radio emission has been detected from ground-based observations since the 1950s.

Voyager 1 and 2 ultraviolet spectrometers unequivocally identified H2 Lyman and

Werner bands and H Ly-α emissions from Jupiter’s polar regions (Broadfoot et al.,

1979). Shortly after the Voyager encounter with Jupiter, the IUE confirmed that the

auroral UV emissions (Clarke et al., 1980). Visible auroral images were first taken

by the imaging experiment on Voyager 1 (Smith et al., 1979), and then soft X-ray

emissions were detected by the Einstein Observatory (Metzger et al., 1983). The

spectroscopic observations of the Jovian UV aurora with the HST were first made

by Trafton et al. (1994). Recently, Gladstone et al. (1998) extensively observed

140 Y. Itikawa et al.

the Jovian X-ray emissions with ROSAT. High-quality X-ray auroral images of

the Jovian planets are expected with the Chandra X-ray telescope launched in

1999.

Voyager/IRIS spectra taken from the northern auroral region of Jupiter showed

several weak emission structures, which were later identified as C2H4, C3H4, and

C6H6 by Kim et al. (1985). Trafton et al. (1987) observed 2-μm H2 quadrupole

lines in emission over the polar regions of Jupiter. The auroral H2 quadrupole line

emissions were theoretically predicted by Kim and Maguire (1986). Subsequently,

Trafton et al. (1989) detected unidentified strong emission lines at 2.1 μm in

addition to the H2 quadrupole lines near Jupiter’s northern limb. These unidentified

lines were eventually identified as the 2v2 band of H3+ (Fig. 5) by Drossart et al.

(1989) using infrared spectra obtained by the FTS on the CFHT. Maillard et al.

(1990), Oka and Geballe (1990), and Miller et al. (1990) detected the fundamental

band (v2) of H3+ at 3.5 μm in the wide areas of the both polar regions. Subsequently,

Kim et al. (1991) and Baron et al. (1991) successfully obtained auroral images,

which revealed detailed auroral structures. During the impacts of the fragments of

comet SL9 on Jupiter in 1994, Kim et al. (1996) obtained 3.5-μm H3+ emission

FIG. 5. H3+ and H2 emission lines over the polar haze continuum of the auroral regions of Jupiter

(Drossart et al., 1989). All the lines are attributed to the 2v2 band lines of H3+ except a line at 2.1218 μm,

which is due to the S1(1) line of H2.

MOLECULAR EMISSIONS FROM THE ATMOSPHERES 141

spectra of the auroral regions, and they found that the temperatures of the southern

H3+ aurora were normal, suggesting no significant influence of the impacts on

the auroral activities. A comprehensive review of the multispectral nature of the

Jupiter’s aurorae was given by Kim et al. (1998), and here we will not present

detailed descriptions about Jupiter’s aurorae.

Since Jupiter’s magnetosphere contains large amount of sulfur and oxygen ions

from Io, it has been expected that these ions may precipitate on to the Jupiter’s

auroral regions. Recently, Trafton et al. (1998) searched for heavy-ion precipitation

with HST, and found no evidence of heavy-ion features in the auroral spectra. They

detected an unidentified feature near 1254 Å at the 4-σ level, which might have

been the suspected SII line at 1256 Å in the low-resolution IUE spectra of Waite

et al. (1988).

The Galileo orbiter has been revolving around Jupiter and its satellites since its

arrival in December 1995. During the passages near Jupiter, the Galileo orbiter has

observed Jupiter’s aurorae with the solid-state imager (SSI), the extreme ultraviolet

spectrometer (EUVS), and the ultraviolet spectrometer (UVS). The SSI has ob-

served prominent visible aurora on the night side of Jupiter (Ingersoll et al., 1998).

The SSI has taken images of the visible aurora with red, violet, green, methane,

and clear filters. Ajello et al. (1998) analyzed Galileo EUV and FUV spectra taken

simultaneously at both the north and south polar regions. The Galileo UVS has ob-

served Jupiter’s aurorae in the near-ultraviolet (NUV) and mid-ultraviolet (MUV)

ranges for the first time. Pryor et al. (1998) analyzed the MUV auroral spectra

using, James et al.’s (1998) laboratory spectra.

Prior to the Voyager 1 and 2 encounters with Saturn, IUE and Pioneer ob-

servations suggested the presence of aurorae on Saturn, but both observations

were inconclusive. Analyzing the spectra of polar regions observed by the Voyager

UVS, Broadfoot et al. (1981a,b) reported clearly defined aurorae. The Voyager

UVS detected an aurora of Uranus near the magnetic pole (Broadfoot et al., 1986).

Broadfoot et al. (1989) tentatively identified faint aurora from the dark side of

Neptune based on Voyager 2 UVS data.

Since the initial detections of the UV aurorae on Saturn, Uranus, and Neptune

by Voyager 1 and 2, there have been a few recent developments in the investigations

of these aurorae—Geballe et al. (1992) first reported the detection of H3+ emission

from Saturn. A dark auroral oval on Saturn was discovered in a 2200-Å band in

HST/FOC UV images (Ben Jaffel et al., 1995). Trafton et al. (1993) reported

detection of H3+ emission from Uranus. They found that the emission intensity

was greater than that of Saturn. Trafton et al. (1995) detected auroral H2 emission

at 2 μm from Uranus. Subsequently, Lam et al. (1997) obtained 2-μm H2 emission

images of Uranus.

In the planetary auroral regions, precipitating particles from the magnetosphere

cause electronic and vibrational excitations of atmospheric species. In order to

142 Y. Itikawa et al.

cross sections of all those electronic and vibrational states of the atmospheric

species upon collisions with the precipitating particles. The energies of precipi-

tating particles decrease due to multiple collisions with the atmospheric species,

and at the same time secondary electrons and ions are produced from the colli-

sions. The excitation rates for the various states of atmospheric molecules and

atoms have been calculated by sophisticated computer programs (e.g., Bisikalo

et al., 1996). For the calculations, cross-section data are needed for all the colli-

sion processes expected between precipitating particles (e.g., electrons, protons,

or ions) and planetary molecules. Cross sections for the electronic excitation

or ionization for molecules in the giant planets, perhaps except for H2, H, He,

and CH4 (e.g., Kim, 1988), are not well known. Particularly important molecules

are C2H2, C2H4, C2H6, C3H8, C3H4, and C6H6. Eventually, the primary and sec-

ondary particles slow down and stop near the bottom of the planetary ionospheres.

The low-energy electrons efficiently excite the rovibrational states of molecules.

Electron-impact vibrational or rotational cross sections of H2 and CH4 have been

measured previously in laboratories. However, those for other molecules, C2H2,

C2H4, C2H6, C3H8, C3H4, and C6H6, by electron, proton, and ion collisions are

scarcely known.

Pure rotational excitations of molecules by electrons are not very important

in the auroral regions of the giant planets, because of high atmospheric densities

in the auroral ionospheres. In the ionospheres of the giant planets, the ground

rotational states of CH4 and H2 are in local thermodynamical equilibrium (LTE),

because rotational deexcitation rates by collisions with H2 and CH4 are signifi-

cantly greater than rotational Einstein A coefficients, which are almost zero for a

spherical-top molecule such as CH4 and for homonuclear diatomic molecules such

as H2 and N2. However, the vibrational states of these molecules are in non-LTE,

because the vibrational deexcitation rates by neutral collisions are approximately

equal to or less then vibrational Einstein A coefficients. Since the ground states

are the dominant reservoir of the CH4 and H2 population, the rovibrational states

should approximately follow the rotational population of the ground states, and the

rotational temperature derived from the observed emission intensities of the rovi-

brational states should approximately represent the ground rotational temperature,

which in turn represents the local kinetic temperature of the ionosphere.

The excited atmospheric species lose their energies via radiation and/or col-

lisions with other species. The last stage of the auroral particle precipitations is

the thermalization of the auroral atmosphere, emitting infrared radiation through

rovibrational bands of molecules. In order to calculate infrared emissions from

molecules and ions, we need cross sections for vibrational–vibrational (v–v)

and vibrational–translational (v–t) energy transfers between vibrationally excited

species and other surrounding molecules/ions. For v–v and v–t energy transfer rates

MOLECULAR EMISSIONS FROM THE ATMOSPHERES 143

of H2 with H2, He, and H collisions, and of CH4 with H2, He, N2, O2, and CH4

collisions are partially available. However, the v–v and v–t rates of C2H2, C2H4,

C2H6, C3H8, C3H4, and C6H6 by collisions with H2, He, H, CH4, etc., are scarcely

available in literature, especially at low temperatures in the planetary atmospheres.

Some crude theoretical models are often used to estimate the energy transfer rates,

but their results contain large ambiguities. Comprehensive quantum mechanical

formulas, which can be used readily by scientists in other fields, are needed.

E. TITAN

The existence of Titan’s atmosphere was first recognized spectroscopically by

Kuiper (1944), who discovered gaseous CH4 (methane). Almost three decades later,

a tentative detection of H2 in the visible range, and a probable detection of C2H6

(ethane) at 12.2 μm were reported. A model atmosphere with a large temperature

inversion was proposed (e.g., Danielson et al., 1973). Additional hydrocarbon

bands of C2H2, C2H4, and a deuterated methane, CH3D, were positively detected

in emission in the range 7.8–13.3 μm along with the C2H6 band (Gillett, 1975).

Unlike ground-based telescopes, which barely resolve the Titan disk, the IRIS

on the Voyager 1 and 2 spacecraft obtained spatially resolved infrared spectra in

the range 5–50 μm (e.g., Hanel et al., 1981). The Voyager IRIS team identified

emissions bands of C3H4 (methyl acetylene), C3H8 (propane), and HCN (hydro-

gen cyanide) in the spectra of equatorial and temporal regions of Titan. In the

spectra of north polar regions, where dark haze layers were clearly seen in visible

images, additional molecules, C4H2 (diacetylene), C2N2 (cyanogen), and HC3N

(cyanoacetylene), were identified by the IRIS team. The detections of the several

nitrogen-containing molecules confirmed the N2-dominant atmosphere, which was

first recognized by the results from extreme UV observations of N2 emissions

(Broadfoot et al., 1981b), and from radio occultation experiment (Tyler et al.,

1981) on Voyager 1. The N2-dominant atmosphere was remarkably similar to an

atmospheric model of Titan proposed by Hunten (1978). Further detailed analyses

of the IRIS spectra revealed a CO2 emission band, a dominant CH3D feature at

8.6 μm over a C3H8 band feature there, and a C4N2 ice band. A ground infrared

observation also yielded a CO band in absorption at 1.6 μm (Lutz et al., 1983).

Recently, Kim et al. (2000) detected 3-μm emission lines of the v3 and

v3+v4−v4 bands of CH4 from Titan’s high-altitude atmosphere using the CGS4 on

the UKIRT (Fig. 6). Analyzing the spectrum, they found that the CH4 emissions

form mainly in the 530–630 km altitude range, where temperatures are 137–145 K,

consistent with a low-temperature mesosphere as proposed by Yelle (1991). It is

surprising that the emission intensity of the weak combination band is comparable

to that of the strong v3 fundamental band, and that this is also the case for Jupiter

and Saturn (Drossart et al., 1999).

MOLECULAR EMISSIONS FROM THE ATMOSPHERES 145

This section reviews the emission spectra of comets. The spectra in the ultravi-

olet/visible, infrared, and radio ranges are described in Sections III.A, III.B, and

III.C, respectively. Section III.D summarizes isotopic abundances derived from

the observed spectra of cometary comas. Most of the cometary emissions are

arisen as a fluorescence of the solar radiation. Collisions among the atmospheric

constituents (i.e., atoms, molecules, radicals, ions, and electrons), however, have

sometimes significant effects on the fluorescence spectra. These collisional pro-

cesses are discussed in Section III.E.

Since Swings et al. (1941) began spectroscopic observations of comets in the

visible range, parent molecules in cometary nuclei have been considered to be pris-

tine, keeping information about elemental abundances in the presolar nebula. The

visible range, however, hardly shows parent molecules, but mostly shows radical

emissions. The abundances of parent molecules in the nuclei have been indirectly

inferred from the radical abundances observed by using laboratory and/or theoreti-

cal data on chemical reactions between molecules, radicals, and ions. The inferred

abundances of parent molecules from various spectral ranges have been com-

pared with those in interstellar media (e.g., Bockelée-Morvan et al., 2000; Irvine

et al., 2000). Chemistry models of various interstellar media have been significantly

improved during the last decade by theorists who have been trying to explain the el-

emental abundances observed in interstellar ices (e.g., Fegley et al., 1997; Aikawa

et al., 1999; and references therein). The comparisons between abundances of

cometary molecules and those of interstellar ices (e.g., Bockelée-Morvan et al.,

2000; Irvine et al., 2000) show that there is an intimate similarity suggesting the

interstellar origin of the cometary material.

Comets produce abundant atoms, molecules, radicals, and ions. Some radicals

in cometary comas could not be identified immediately because corresponding

laboratory spectra were not available. Since free radicals are extremely reactive, it

has not been easy to obtain their spectra in laboratories [e.g., see the introduction

section of Herzberg (1971)]. Indeed, the identification of the radical bands has been

difficult, often took many years, and sometimes was not correct. For example, the

4050 Å band was first discovered in 1881 by Huggins (1882), but it was not

correctly identified for 70 years. The band even confused a Nobel Prize laureate,

FIG. 6. (Top) Spectrum of Titan obtained on 1999 September 14 (UT) (Kim et al., 2000). Strong

telluric absorption by the Q-branch lines of the CH4 v3 band blocks Titan’s Q-branch emission. The

S/N ratios at the peaks of typical v3 and the v3+v4−v4 lines are estimated to be 2–4 and 8, respectively.

(Bottom) A model spectrum, including the v3 and v3+v4−v4 bands with a rotational temperature of

140 K. The long vertical lines indicate the positions of the v3 band lines, some of which are blended

with the lines of the v3+v4−v4 band. The short vertical lines and other weak features are all identified

as those of the v3+v4−v4 band. Only the v3 lines are labeled.

146 Y. Itikawa et al.

G. Herzberg, who attributed the 4050 group to a band of CH2 (e.g., Herzberg, 1942).

It was ultimately identified as the bands of C3 by Clusius and Douglas (1954).

Observations of comets in the ultraviolet were begun by using sounding rockets

and space-borne observatories (e.g., Feldman et al., 1974). The detected strong

H I Ly-α envelope and OH emission at 3085 Å confirmed the icy conglomerate

model, “dirty snowball model,” for cometary nuclei proposed by Whipple (1950,

1951). Since 1978, the IUE has been active in the observations of comets, most

notably comet P/Halley, during its operation period of nearly 18 years. Strong

atomic emissions of H, C, S, and O; radical emissions of CS, OH, and a weak C2

band; and ionic emissions of CO2+ have been usually shown in UV spectra. Before

the bright comets Hyakutake and Hale–Bopp, the only comet which exhibited S2

emission in the UV region was comet IRAS–Araki–Alcock 1983VII (A’Hearn

et al., 1983).

In the visible range (3000–9000 Å), radicals, such as OH, NH, CH, CN, C2,

C3, NH2 (e.g., Arpigny et al., 1991; Brown et al., 1996); ions, such as CO+, OH+,

CH+, H2O+, N2+, CO2+ (e.g., Wyckoff et al., 1996); and only one stable molecule,

S2 (Fig. 7; Kim et al., 1990), have been observed. During the last five decades,

the spectral resolving power (λ/δλ) of spectrometers in the visible range has been

increased from an order of ∼1000 (Swings et al.,1941; Dossin et al.,1961) to

∼100,000 (Brown et al., 1996) nowadays. The high-resolution spectroscopy in

the visible range provides a wealth of emission lines from the radicals, making it

possible to investigate detailed fluorescence and collision excitation processes of

the radicals in cometary comas (e.g., Schleicher and A’Hearn, 1982; Kim et al.,

1989); and to separate isotopic molecular lines from adjacent normal molecular

lines (e.g., Kleine et al., 1994 ,1995). On the other hand, Brown et al. (1996) listed

hundreds of unidentified lines between 3800 and 9900 Å. Wyckoff et al. (1996)

also reported unidentified lines in the plasma tail spectra of P/Halley.

Schleicher and A’Hearn (1982, 1988) constructed a fluorescence model of OH

bands that appeared in the IUE high-dispersion spectra of comets in the near-UV

range, which can also be observed from the ground. Kim et al. (1989) constructed

an A–X (0–0) band model of NH, which occurs in the range 3345–3375 Å of

P/Halley spectra. They found that the NH spectrum is due to pure fluorescence

with negligible influence by collisions. Gredel et al. (1989) updated the C2 band

model of A’Hearn (1978) and compared it with the high-resolution spectra of

P/Halley, and the fit was satisfactory. However, the authors pointed out that the ac-

curate determinations of the transition probabilities of the electronic bands should

improve their model significantly.

In cometary comas, molecular number densities are usually less than those

of planetary ionospheres or thermospheres, so collision deexcitation rates are in-

significant in fluorescence processes. Therefore, molecules in cometary comas are

MOLECULAR EMISSIONS FROM THE ATMOSPHERES 147

FIG. 7. The solid line is a ground-based spectrum of comet IRAS–Araki–Alcock 1983VII between

3050 and 4350 Å, and the dashed line is a fluorescent equilibrium model described by Kim et al. (1990).

The identified B–X bands of S2 in the observed spectrum are marked by ∗ .

mostly in non-LTE except for the regions very close to the surfaces of massive

outgassing comets, such as comet Hale–Bopp. Note that in pure fluorescent equilib-

rium, ground-state populations are constantly redistributed mainly by fluorescence

transitions from upper states, and thus the ground rotational state populations can-

not represent the local kinetic temperatures.

Among the detected neutral radicals in the range 3000–9000 Å, line-by-line

spectral structures of NH2 and C3 bands have not been modeled in detail. NH2 is

an asymmetric top molecule, and therefore its band structure is very complicated

compared with other linear and symmetric molecules. While line-by-line quantum-

number designations of the NH2 A–X bands, have been carried out by Dressler and

Ramsay (1959), Johns et al. (1976), and in unpublished works by spectroscopists

at the Herzberg Institute of Astrophysics, a complete line list of the A–X bands

including high J lines has not been available thus far. Furthermore, individual line

transition probabilities of the bands have not been completely determined either,

although vibrational transition moments and lifetimes have been discussed by

Jungen et al. (1980), and Einstein A coefficients for certain rotational lines of the

(0,9,0)–(0,0,0) and (0,8,0)–(0,0,0) transitions have been calculated by Kawakita

148 Y. Itikawa et al.

et al. (2000). The lack of accurate transition probabilities prevents the development

of a proper fluorescence model for the NH2 bands.

The situation for the C3 bands is even worse. Although Gausset et al. (1965)

listed quantum-number designations for strong lines, the list lacks weak line des-

ignations, especially for the spectral range 3880–3950 Å, where the strong B–X

band of CH occurs (Kim et al., 1997a) and the strong lines of the A–X band

of CO2+ (Kim, 1999) also occur (Fig. 8). Furthermore, the line list of Gausset

et al. does not provide line intensities and therefore transition probabilities, which

are important parameters used for the derivations of C3 abundances in comets. In

the 3880–3950 Å range of cometary spectra, there are many unidentified lines,

some of which are expected to be due to weak lines of the C3 bands. In order

to properly model the B–X band of CH and the A–X band lines of CO2+, it is

important to clear out those unidentified lines in this spectral range. Since the NH2

and C3 bands are the most prominent emission structures, usually appearing in

the wide spectral range of cometary visible spectra, models of these bands are

urgently needed to properly analyze high-resolution visible spectra of the recent

bright comets.

FIG. 8. Comparison of the best-fit model (solid line) and a tail spectrum (dashed line) of comet

P/GZ observed in 1985 with a spectral resolution of 20 Å (Kim, 1999). The NH band is blended with a

CO2+ band. The negative intensities occur because atmospheric transmission rapidly decreases toward

shorter wavelengths, and the negative intensities in the GZ spectrum indicate the degree of uncertainties

in the comet spectrum.

MOLECULAR EMISSIONS FROM THE ATMOSPHERES 149

Among the detected ions, CO+, OH+, CH+, H2O+, N2+, CO2+, only the bands

of two ions, CO+ and CO2+, have been modeled. Magnani and A’Hearn (1986)

constructed a fluorescent equilibrium model of the visible bands of CO+, including

Swings and Greenstein effects, which depend on heliocentric radial velocity. Kim

(1999) constructed a fluorescence equilibrium model of the A–X and B–X band

systems of CO2+, and compared the model with the spectra of comets Austin

(1989c1) and P/Giacobini–Zinner (GZ) (Fig. 8). The model, however, includes

only vibrational–vibrational transitions, ignoring rotational transitions. In order to

construct the line-by-line model of the CO2+ bands, accurate line positions and

line transition probabilities are needed. Wyckoff et al. (1996) reported unidentified

lines, which are fairly strong and presumably due to ionic lines, in the spectra of

plasma tails of several comets. Bands of other ionic molecules, such as OH+, CH+,

H2O+, and N2+, are awaiting modeling for use in the analyses of plasma tail spectra

and in the identification of those unidentified lines.

B. INFRARED SPECTRA

Before P/Halley, the low-resolution spectroscopy of comets in the infrared region

yielded only continuum emissions of dust and/or ice through the 3-, 10-, and 20-μm

atmospheric windows (e.g., Tokunaga et al., 1984). Recently, spectroscopic obser-

vations of comet Hale–Bopp made by the ISO produced a spectacular panorama

of the infrared spectrum of dust particles covering the range 7–45 μm (Crovisier

et al., 1997). The spectral structure of the dust spectrum has been found to be

remarkably similar to that of Mg-rich olivine-like forsterite (Crovisier, 1998).

The FTS on the NASA/Kuiper Airborne Observatory (KAO) successfully re-

solved individual lines of the 2.65-μm band of H2O in the coma of P/Halley

(Mumma et al., 1986). A low-resolution infrared spectrometer (IKS) on the Vega

spacecraft also detected molecular emissions from the bands of H2CO, CO2, and

possibly CO, in addition to the H2O band in the 2.5–5 μm region of P/Halley

(Moroz et al., 1987). After P/Halley, Hoban et al. (1993) detected emission lines

of the 3.52-μm band of CH3OH in comet P/Swift–Tuttle.

The recent bright comets Hale–Bopp and Hyakutake with high-resolution in-

frared spectroscopy provided opportunities to detect several parent molecules un-

ambiguously. In particular, symmetric molecules, such as CH4, C2H6, and C2H2

having no permanent electric dipole moment could not be detected by radio obser-

vations. Mumma et al. (1996) positively detected infrared lines of C2H6, CH4, and

CO in the coma of Hyakutake. They found an abundant C2H6/CH4 ratio, which is

consistent with the production of C2H6 via hydrogenation of C2H2 on grain sur-

faces, or UV photolysis of ice mixtures in interstellar clouds (Mumma et al., 1996;

Hasegawa and Herbst, 1993), and not consistent with a thermochemically equili-

brated region in the proto-solar nebula (e.g., Prinn and Fegley, 1989). Almost at the

same time as Mumma et al. (1996), Brooke et al. (1996) observed Hyakutake and

150 Y. Itikawa et al.

FIG. 9. The plots show CSHELL/IRTF spectra (solid line) of comet Hale–Bopp in the regions having

gaseous emissions from H2O, CH4, C2H6, C2H2, CO, and HCN (Weaver et al., 1997). The spectra have

not been corrected for atmospheric transmittance; gases in the terrestrial atmosphere produce the many

observed absorption features. The gaseous emissions are superimposed on a strong continuum emitted

by the cometary grains, which have been modeled (dashed line).

detected the 3-μm band lines of C2H2. The same molecular species, H2O, CH4,

C2H6, C2H2, and CO, in addition to HCN were detected in Hale–Bopp (Fig. 9;

Weaver et al., 1997). OCS was first detected in Hyakutake in radio (Woodney

et al., 1997), and subsequently in Hale–Bopp in infrared at 4.85 μm (Dello Russo

et al., 1998). The ratio of the OCS production rates relative to water production

rates are 3 × 10−3 for Hyakutake (Woodney et al., 1997), and 3–5 × 10−3 for

Hale–Bopp (Dello Russo et al., 1998).

Recently, Weaver et al. (1999) observed comet 21P/GZ and found that C2H6

is depleted at least by a factor of ∼10 compared to its relative abundances in

Hale–Bopp and Hyakutake. This depletion is similar to that observed for C2 and

C3 from optical observations of GZ (A’Hearn et al., 1995), suggesting that the

MOLECULAR EMISSIONS FROM THE ATMOSPHERES 151

same time, Mumma et al. (2000) also observed comet 21P/GZ, and found that

C2H6 is substantially less abundant compared with Hale-Bopp and Hyakutake.

Recent Keck observations (Mumma et al., 1999) of comet C/Lee provide high

signal-to-noise-ratio spectra in the range 1–5.5 μm showing many unidentified

lines, which are awaiting identification.

C. RADIO SPECTRA

Until the positive detections of millimeter lines of H2CO, H2S, and CH3OH in

several comets reported by Bockelée-Morvan et al. (1991) and Crovisier et al.

(1991) in the early 1990s, radio observations of comets were not very successful.

The only parent molecule unambiguously detected in the microwave range before

1990 was HCN in comets P/Halley and Kohouteck 1973 XII (e.g., Schloerb et al.,

1987). The radio spectra of the recent bright comets Hyakutake and Hale–Bopp

yielded an avalanche of new parent molecules: NH3, HDO, HNC, CH3CN, CS2,

and possibly OCS and HNCO from Hyakutake; and HCOOH, HCOOCH3, HC3N,

NH2CHO, SO, SO2, H2CS, and positively OCS and HNCO from Hale–Bopp

(Fig. 10). (For summaries and reviews of these detections, see Lis et al., 1997;

Crovisier and Bockelée-Morvan, 1999; Bockelée-Morvan et al., 2000).

One of the surprises from these observations was the detection of SO and

SO2, as very stringent upper limits on their abundances in comets were deter-

mined previously from UV observations (Kim and A’Hearn, 1991). Recently, Kim

et al. (1997b), using updated information available in the literature, found that Kim

and A’Hearn (1991) overestimated the solar excitation rate of the UV transition

of SO by ∼2 orders of magnitude using an erroneous radiative lifetime available

at that time in the literature. For SO2, the nondetection in the UV range is still

in question. Since the UV band of SO2 has not been sufficiently analyzed in the

literature, detailed laboratory and theoretical analyses of the band are needed to

resolve this issue.

The derived abundances of parent molecules in Hyakutake and Hale–Bopp

are found to be approximately consistent with those inferred in interstellar ices,

hot cores of molecular clouds, and bipolar flows around protostars (e.g., Bockelée-

Morvan et al., 2000; Irvine et al., 2000). The derived abundances from radio obser-

vations along with results from infrared observations suggest that cometary mate-

rial was mainly formed by similar nonequilibrium processes as produce interstellar

ices: grain-surface reactions, condensation of products of ion–molecule reactions,

and UV processing. The subsequent process during the planetary formation in

the proto-solar nebula did not seem to significantly influence the compositions of

the cometary material (e.g., Bockelée-Morvan et al., 2000). These new findings

become a great challenge to theorists—the nonequilibrium chemical models of

Willacy et al. (1998) and Finocchi et al. (1997) produce molecular abundances

152 Y. Itikawa et al.

FIG. 10. Millimeter spectra of Hale–Bopp containing emission lines of SO (observed at Caltech

Submillimeter Observatory, CSO), SO2 (Institut de Radioastronomie Millimétrique, IRAM, Plateau-

de-Bure interferometer, PdB), OCS (CSO), HC3N (CSO), HNCO (CSO), NH2CHO (IRAM 30-m),

HCOOH (IRAM PdB), and HCOOCH3 (IRAM 30-m) (Bockelée-Morvan et al., 2000). The velocity

frame is with respect to the comet nucleus velocity. The dashed line superimposed on the observed

spectrum of HCOOCH3 is a synthetic profile calculated using HC3N line at 227.419 GHz observed

at the same time. It takes into account that the HCOOCH3 line at ∼225.562 GHz is a blend of eight

transitions whose positions are shown.

MOLECULAR EMISSIONS FROM THE ATMOSPHERES 153

in the inner part of the proto-solar nebula, which are significantly different from

those of comets.

D. ISOTOPIC ABUNDANCES

Kleine et al. (1995) derived a 12C/13C ratio of 95 ± 12 analyzing high-resolution

CN spectra of P/Halley between 3860 and 3890 Å, and the result agrees with the

solar ratio of ∼90. The agreement suggests that comets should be coevolved from

the same molecular cloud as other members of the solar system. The recent bright

comets Hale-Bopp and Hyakutake yielded high-signal-to-noise-ratio spectra of

radicals in the visible region (Cochran et al.,1997; Meier et al.,1998a). Meier

et al. (1998a) analyzed high-resolution spectra of the NH (3340–3380 Å) and

CH (4280– 4340 Å) bands of Hyakutake, and derived upper limits of ND/NH

and CD/CH (Fig. 11) ratios, which are 6 × 10−3 and 3 × 10−2, respectively. Millar

et al. (1989) investigated gas-phase chemistry including ion–molecule interactions

in dense interstellar clouds in order to study deuterium fractionations of various

molecules. According to their model calculations, the ND/NH and CD/CH ratios

FIG. 11. Measured (top) and modeled (bottom) A–X (0–0) bands of CH and CD of comet Hyakutake

(Meier et al., 1998a). Solid lines represent CH features and open lines belong to CD lines. Note that

the modeled spectrum has a different y scale than measurements.

154 Y. Itikawa et al.

spectively, and these ratios are significantly greater than the HD/H2 ratio, which

is ∼ 3 × 10−5.

Isotopic molecules, such as HDO and H13CN in Hyakutake, and DCN, H13CN,

HC15N, and C34S in Hale–Bopp, were also detected in the radio range (e.g.,

Bockelée-Morvan 1998; Meier et al., 1998b, 1998c; Crovisier and Bockelée-

Morvan, 1999). The derived D/H ratios in H2O from the H2O and HDO radio

lines of Hyakutake and Hale–Bopp as well as the D/H ratio of P/Halley measured

from a mass spectrometer on the Giotto spacecraft are all ∼3 × 10−4. This value

is approximately consistent with observed D/H ratios in the hot cores of molecular

clouds, but lower than those measured in carbonaceous meteorites and interstel-

lar ices. The lower D/H ratios in comets than in interstellar ices suggest that the

diffusion process in the warm inner part of the proto-solar nebula partially diluted

the originally higher ratios in the interstellar ices (Bockelée-Morvan et al., 1998,

2000; Irvine et al., 2000). The D/H ratios from the three comets are clearly ∼2

times higher than terrestrial standard mean ocean water (SMOW).

The D/H ratio in HCN derived from HCN and DCN lines is 2.3 × 10−3 (Meier

et al.,1998b), and the ratio is in the range reported in the hot cores of molecular

clouds (Hatchell et al.,1998). The derived ratio is consistent with results from

interstellar ion–molecule chemistry model (Millar et al.,1989). The hot cores,

however, might be too young to reach the steady state, and the observed ra-

tio might have been diluted from an originally higher value of interstellar ices

(Hatchell et al.,1998). Therefore, additional observations, laboratory, and theo-

retical works are needed to clarify the connection between the cometary mate-

rial and the interstellar matter. The isotopic ratios of carbon, nitrogen, and sulfur

appear to be cosmic, because the fractionations of heavy species, such as car-

bon, nitrogen, and sulfur, are less sensitive to chemical reactions in cometary

nuclei.

As shown from the above OH and NH research in the visible spectroscopy, the

rotational structures of the radicals may be influenced by collisions with neutrals

and electrons in the cometary environment. The difficulty in applying the colli-

sion influences to the spectral structures is that experimental results on the cross

sections of the radicals are very limited in the literature. In particular, rotational

excitation rates of cometary molecules via collisions with cometary molecules

are poorly known. Only several cases, such as H2O <− (excited by) H2, CO <−

H2O, CO <− N2, N2 <− H2O, etc., have been investigated in detail by S. Green

(e.g., Phillips et al., 1996; Green, 1993, 1995; references therein), whose untimely

death prevented further progresses in this important area. S. Green constructed

cross sections theoretically. The theoretical results were tested by experimental

measurements of pressure-broadening line widths, although the experimental line

MOLECULAR EMISSIONS FROM THE ATMOSPHERES 155

widths are not sufficient to generate the excitation rates inversely. Since the most

abundant neutral species in comas are H2O, OH, and CO, the collision cross sec-

tions of cometary radicals with these neutrals at coma temperatures (10–500 K)

are needed. In order to calculate collision frequency, neutral densities of H2O,

OH, and CO are needed. The OH density, which should be similar to the H2O

density, has been measured in the coma of comet P/Halley by instruments on

Vega and Giotto (e.g., Fig. 4 of Kim et al., 1989). The rotational excitations by

molecule–molecule collisions are important only in inner coma regions, where

neutral densities are sufficiently high to excite or deexcite the cometary molecules

compared with other excitation processes, such as electron collisions and radiation

excitations.

Electron densities in the outer coma region (1 × 104 to 9 × 105 km from the

nucleus) of P/Halley as a function of cometocentric distance were measured by

Vega 1 and 2 (Pederson et al., 1987). Kinetic energies (which can be translated into

kinetic temperatures) of electrons for P/Halley were also derived to be 0.5–1.0 eV

in the outer coma region (Pederson et al., 1987). An ion mass spectrometer on

Giotto measured ion densities, which may be used as electron densities assuming

an overall charge neutrality in the inner coma region (103–104 km) of P/Halley.

In the outer coma regions, where neutral densities decrease exponentially, colli-

sions with electrons become significant (e.g., Fig. 4 of Kim et al., 1989). Infor-

mation on electron impact cross sections for rotational excitations of cometary

molecules is very limited. In particular, virtually no experimental data are avail-

able for these processes so far. A few approximate theoretical methods have been

proposed for the calculation of the rotational cross sections, but their reliability is

uncertain.

The rotational excitations and deexcitations of cometary molecules by colli-

sions with electrons, ions, and neutrals equally influence the rotational structures

of the ultraviolet and visible (electronic), infrared (rovibrational), and radio (pure

rotational) bands. It is also noted that vibrational or rovibrational excitations of

molecules by electrons, ions, or neutrals are not very important in cometary co-

mas compared with excitations by solar infrared radiation, but these vibrational

transitions are important processes in planetary auroral regions, as mentioned in

Section II.D. For a massive comet, such as Hale–Bopp, the vibrational deactivation

rates of cometary molecules by collisions with water molecules near the nucleus

is significant compared with vibrational Einstein A coefficients of the cometary

molecules, and, therefore, a LTE state can be formed near the nucleus.

Analysis of observed spectra relies largely on available spectral databases. These

databases, however, are not sufficient for the analysis of the planetary or cometary

spectra. In this section we propose possible improvements of the spectral databases.

156 Y. Itikawa et al.

Since the early 1980s, spectroscopists at the Air Force Geophysical Laboratory

(AFGL), the Goddard Space Flight Center (GSFC), the Jet Propulsion Labora-

tory (JPL), and the Centre National de la Recherche Scientifique (CNRS) have

constructed/compiled spectroscopic databases (the HITRAN, MLA, ATMOS, and

GEISA databases, respectively) in standardized formats mainly for infrared lines

of the molecules mostly in the Earth’s atmosphere (e.g., Rothman et al., 1987;

Bjoraker et al., 1986; Brown and Toth, 1985; and Husson, et al., 1986, respec-

tively). These databases accommodated available spectroscopic line parameters

published in the literature, and added new spectroscopic information generated

by the spectroscopists in their institutions. Thus, the majority of the line informa-

tion in these databases overlaps each other. In the submillimeter, millimeter, and

centimeter ranges, Poynter and Pickett (1985) have been compiling spectroscopic

parameters for more than 100 molecules and atoms.

Although the above spectroscopic databases have been continually updated by

the authors over the last 20 years, planetary scientists frequently find that needed

spectroscopic parameters for certain molecules are not included in the databases.

For example, line positions, quantum-state designations for the lines, line inten-

sities, line widths, and lower-state energies, which are basic information to be

used for the analyses of planetary spectra, are very poorly known for the over-

tone and combination bands of hydrocarbons, such as C2H2, C2H4, C2H6, C3H8,

C3H4, C4H2, and C6H6; the nitrogen-containing molecules NH3 and HCN; and

molecules containing heavy elements, such as H2S, AsH3, GeH4, and PH3. Even

for H2O, CO2, CO, and CH4, which are relatively well studied compared with the

above molecules, the spectroscopic parameters for the overtone and combination

bands are not completely studied. The intensities of far-infrared bands are severely

affected by hot bands due to their relatively low energy states. The intensities of

far-infrared fundamental bands are often substantially lower than the total hot band

intensities even at room temperature. The hot band influence is significant even in

outer planets’ cold environment (60–150 K). Some of the fundamental bands of

C2H2, C3H4, C4H2, C6H6, CO2, and H2O occur at wavelengths longer than 10 μm,

where hot band intensities become significant. The spectroscopic parameters for

these hot bands are available only in part, with the exception of CO2 and H2O.

As we discussed in Section II.B, we expect to detect additional airglow emissions

from the bands of CH4 and other hydrocarbons in planetary atmospheres. The most

extensive compilation of these CH4 band transitions can be found in a recent work

of Wenger and Champion (1998), who listed absorption line intensities of the CH4

bands. For the analysis of the emission lines, we need Einstein A coefficients for

individual line transitions. Although Einstein A coefficients for individual lines

can be calculated from the absorption line intensities using Eq. (2–17) of Penner

(1959), it is not usually straightforward to obtain the Einstein A coefficients. For

speedy analyses of planetary airglow emissions, we need a column of Einstein A

coefficients for planetary molecules in the databases, such as HITRAN, ATMOS,

GEISA, etc.

MOLECULAR EMISSIONS FROM THE ATMOSPHERES 157

V. Conclusions

The successful spectroscopic observations of atmospheric molecules in the atmo-

spheres of the giant planets, Titan, and comets, and the derived elemental abun-

dances in these atmospheres during the last three decades leave a fundamental

task for planetary scientists—how to explain the origin and chemical evolution

of the solar system bodies based on the derived elemental abundances. The cur-

rent elemental abundances of the giant planets support a planetary formation sce-

nario that the cores and atmospheres of the giant planets were made from accre-

tions of icy planetesimals and from the capture of gases from the surrounding

proto-solar nebula. The current elemental abundances derived from comets

Hyakutake and Hale–Bopp are approximately consistent with molecular abun-

dances derived from interstellar ices, hot cores of molecular clouds, and a subse-

quent planetary formation process. There have also been active spectroscopic and

image observations of aurorae and airglows on the giant planets. However, detailed

auroral and airglow processes are not clearly determined compared with those of

Earth’s aurorae and airglows, partially due to lack of information on the collision

cross sections of auroral molecules. Hundreds of lines in cometary and planetary

spectra are unidentified. Proper spectroscopic studies of these molecular bands are

urgently needed to identify molecules, and to properly analyze the spectra of the

atmospheres of comets and the giant planets. Additional laboratory and theoretical

works are essential to improve the current solar system formation scenario and to

better understand auroral and airglow processes. Success of planned future mis-

sions and ground-based observations as well as further theoretical and laboratory

studies of molecules will provide significant progress in understanding the origin

and evolution of the solar system, and chemical processes of molecules in the

atmospheres of the giant planets, Titan, and comets.

VI. Acknowledgments

The present review chapter is a product of the cooperative research of the Core Uni-

versity Program on Energy Science and Engineering between the Seoul National

University and the Kyoto University. SJK, YHK, and YCM acknowledge finan-

cial support provided by a grant (1999-1-113-001-5) from the Interdisciplinary

Research Program of the Korean Science and Engineering Foundation. We would

like to thank D. Bockelée-Morvan for providing Fig. 10.

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ADVANCES IN ATOMIC, MOLECULAR, AND OPTICAL PHYSICS, VOL. 47

STUDIES OF ELECTRON-EXCITED

TARGETS USING RECOIL

MOMENTUM SPECTROSCOPY

WITH LASER PROBING OF

THE EXCITED STATE

ANDREW JAMES MURRAY

Department of Physics and Astronomy, The University of Manchester, Manchester M13

9PL, United Kingdom

PETER HAMMOND

Department of Physics, University of Western Australia, Nedlands, Perth WA6907,

Australia

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163

II. Atomic Deflection Using Electron Impact. . . . . . . . . . . . . . . . . . . . . . . 167

A. Principles of the Deflection Technique . . . . . . . . . . . . . . . . . . . . . . 167

B. Experimental Recoil Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . 173

C. Differential Cross-Section Measurements . . . . . . . . . . . . . . . . . . . . 177

III. Doubly Excited States Studied via the Fluorescence Decay Product:

Recoiling Excited Atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... 182

A. Principles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..... 182

B. Experimental Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . ..... 184

C. Observations of Momentum-Analyzed Doubly-Excited-State

Fluorescence Decay Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184

IV. Stepwise Laser Probing of Deflected Metastable Targets . . . . . . . . . . . . . 187

A. Principles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187

B. Experimental Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190

C. Results from Laser Probing of Metastable Targets . . . . . . . . . . . . . . . 192

V. Conclusions and Future Experiments. . . . . . . . . . . . . . . . . . . . . . . . . . 199

VI. Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201

VII. References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202

I. Introduction

Historically, experiments studying electron scattering from gas-phase targets have

overwhelmingly concentrated on detection of the scattered electron. This ex-

perimental bias is due to the relative ease of producing an electron beam in a

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ISBN 0-12-003847-1/ISSN 1049-250X/01 $35.00

164 Andrew James Murray and Peter Hammond

well-defined state prior to the interaction, where the energy and momentum of the

electron are accurately controlled [1, 2]. Further, analysis of the scattered electron

following elastic scattering [3, 4], inelastic scattering [5], or ionization [6, 7] of

the target can be achieved to high accuracy using electrostatic detectors designed

to measure the electron momentum.

It is less usual to detect the target momentum following the interaction, although

by conservation of momentum and energy the same information can in principle

be extracted. As in conventional electron-scattering experiments, it is necessary

to define to high accuracy the initial and final momenta of the target undergoing

the interaction to obtain meaningful results. In most gas-phase experiments, an

effusive beam is employed from either a hypodermic needle or from an oven, and

so the distribution of initial target velocities and directions is not well defined. It

is therefore difficult to accurately determine collisional parameters from the target

momenta in these studies.

Although experiments which measure the target recoil are difficult, they have

been performed for a number of years, since there can be advantages in using

such techniques. Bederson [8] pioneered these studies by employing a target of

well-defined initial momentum and measuring the deflection (recoil) following

electron interaction. Since these initial experiments, Bederson and co-workers

have exploited this technique to measure cross sections for elastic, inelastic, and

superelastic scattering from atoms and for molecules [9–12]. These experiments

measure cross sections in the low-energy regime at forward scattering angles,

where it is difficult to employ conventional techniques because of to the difficulty

of observing electrons scattered in the forward direction.

Bederson and co-workers employ a crossed-beam geometry where the electron

beam and target beam interact at right angles as shown in Fig. 1. The targets,

deflected through a recoil angle α by electrons scattering through an angle θe,

FIG. 1. Recoil of a target in a crossed-beam interaction. The incident target of well-defined momen-

tum interacts with an electron which scatters through an angle θe . Momentum conservation requires

that the target is deflected through an angle α.

STUDIES OF ELECTRON-EXCITED TARGETS 165

are detected simultaneously with the direct, unscattered target beam using the

same detector. It is therefore possible to measure absolute cross sections. These

measurements are constrained to forward electron-scattering angles which are

inferred from the deflected target angles.

Exploitation of a well-defined initial target momentum has also been employed

in a new type of ionization experiment recently invented, known as cold target recoil

ion momentum spectroscopy (COLTRIMS) [13–17]. This technique can produce

large amounts of information, and has been used in electron-impact, ion-impact,

and photoionization studies. A target beam of well-defined initial momentum is

produced, and the momenta of the recoiling ion and electron(s) following the

collision is measured. COLTRIMS experiments can sample the entire momentum

space, and so cross sections that are differential in both energy and angle are

determined. Since the emitted electrons are detected over a 4π solid angle, absolute

measurements can be performed.

One further experiment that exploits the initial target momentum and which

is relevant here is the inelastic electron-scattering process which leaves the target

in a metastable state. In this case, the interaction produces a deflection and the

target is left with internal energy. Momentum and energy are again conserved, and

so it is possible to determine the electron-scattering angle which correlates with

the deflected target. The cross section, differential in energy and angle, can then

be calculated. One advantage of this technique is that the internal energy can be

employed for detection of the neutral metastable target. When a metastable target

interacts with a surface, the internal energy is transferred to the surface and an

electron may be emitted. This electron can be detected with high efficiency using

an electron detector such as a channel electron multiplier (CEM) [18], channel

plate (CP) [19], or discrete dynode electron detector [20]. In many experiments

the internal energy of the target is sufficiently high to directly emit an electron

from the front surface of the detector (around 8 eV of internal energy is required

for most commercial devices [21]). In this case, the detector can be used directly

to measure the neutral metastable atoms. Metastable targets with lower internal

energy can also be detected in collision with heated low-work-function materials,

with the electron emitted from the surface being subsequently detected [22].

A number of experiments have exploited the internal energy of metastable

targets. Brunt et al. [23] and Buckman et al. [24] used a high-resolution electron

source to study short-lived negative ion states that decay by autodetachment to

produce metastable helium. These experiments used an effusive helium beam from

a hypodermic needle, and calculated an average deflection angle from the peak

of the target Doppler profile. The metastable atom detector, consisting of a CEM

with a cone-shaped entrance aperture, was placed at this angle and the total yield

of excited atoms was measured as a function of electron impact energy as shown

in Fig. 2. The cross section was therefore measured differential in energy, with no

angular information being ascertained. A rich variation of metastable yield was

166 Andrew James Murray and Peter Hammond

(From Ref. [24].)

observed as the incident energy varied from threshold to ionization at 24.6 eV,

arising from the decay of temporary negative ion states by autodetachment into

the metastable states, together with cascade contributions from higher states. This

technique has been used to study a variety of different atomic and molecular targets

[25, 26, and references therein].

Metastable atom recoil angular measurements were made by Shpenik and co-

workers [27], who studied electron-impact excitation of metastable levels of all

noble gases. In these experiments the incident target beam momentum was well de-

fined using a supersonic expansion. A cross section differential in energy was there-

fore determined. These authors compared their work with calculations using a close

coupling method, which included effects arising from negative ion states decaying

by autodetachment and cascade contributions from higher-lying states [28–30].

Target recoil experiments which also utilized time-of-flight measurements were

first reported by Pearl et al. [31] and were later extended by Defrance et al. [32].

In molecules, Oshima et al. [33] studied N2 excited to the E 3 g+ metastable state

and H2 excited to the c3u metastable state. In these experiments the time-of-flight

technique was used to measure the momenta of deflected targets, thereby producing

a cross section differential in both energy and angle. It is these experiments that

most closely resemble the work discussed in Sect. II of this chapter.

Finally, it is appropriate to mention new techniques which produce a well-

defined target momentum and which are being used for both scattering and atom

optics experiments. These techniques use resonant laser cooling and manipula-

tion of the target beam momentum, exploiting the interaction of a single-mode

laser beam with the target [34]. In these experiments, the momenta of many

STUDIES OF ELECTRON-EXCITED TARGETS 167

resonant laser photons is transferred to the target in such a way that the target

slows down, and the velocity profile is compressed to a narrow distribution. The

velocity can also be reduced in a direction orthogonal to the target beam direction,

producing a high-brightness beam [35–37]. The interaction is controlled using

the polarization, power, and detuning of the laser beam. It is possible to produce

a slow, intense beam of atoms which can be used for atom optics experiments

[38], atom interferometers [39], atom trapping [40], atom cooling [41], Bose–

Einstein condensation experiments [42], and for electron-scattering experiments.

These laser cooling and compression techniques promise to open up new avenues

which exploit the momentum of the target beam. Since the deflection angle fol-

lowing electron impact is inversely proportional to the target momentum, reducing

and controlling this momentum will allow very high-resolution experiments to be

conducted.

In this report, new experiments are described which exploit the metastable

target recoil technique and which also use laser probing of the electron-impact-

excited target to access information unobtainable by other means. To describe

these experiments it is necessary to consider the metastable target recoil arising

from electron impact, and the appropriate equations of motion are introduced in

Sect. II. The experimental apparatus designed and built at Manchester is described,

and results from these studies are presented.

The target deflection technique can also be used to study doubly excited states

of atoms created by electron impact. These experiments are discussed in Sect. III,

and although they are still in their infancy, they are expected to open new avenues

for the study of these very delicate atomic states.

The technique of laser probing the recoiling electron-impact-excited targets is

then discussed in Sect. IV, together with the concept of stepwise resonant laser

excitation and field ionization adopted in these studies. These techniques are used

to probe atomic and molecular targets, and results obtained from these experiments

are presented.

Finally, the direction in which future experiments may proceed is considered

in Sect. V. It is expected that these experiments will use more sophisticated laser

probing techniques, and will exploit the techniques of laser cooling and control of

the initial target momenta. By combining these methods a rich and diverse field of

exploration promises to be opened up in the near future.

When an electron interacts with a target atom or molecule, a number of differ-

ent processes can occur. The electron may scatter elastically from the target, or

the interaction may lead to excitation or ionization. If the target is a molecule,

168 Andrew James Murray and Peter Hammond

fragmentation may also occur. During these processes the total energy and mo-

mentum of the system must be conserved. Hence, if the momenta of the ini-

tial products prior to the reaction are known, the momenta of the final products

are also known. In the work discussed here, the target is excited to a metastable

state, and so internal energy is stored in the target following the reaction. This

energy remains stored until the experiment is concluded, and so it is not nec-

essary to consider effects due to emission of radiation or due to collisional

processes.

Since both energy and momentum are conserved, the recoil deflection of the

metastable target following electron excitation can be determined. It is usual to

derive the equations of motion in the center-of-mass coordinate frame [27, 32],

but it is also possible to derive these in the laboratory frame. This latter approach

is adopted here. In the laboratory frame a coordinate system is defined with the

x axis in the direction of the incident target beam and the z axis in the direction

of the incident electron beam as in Fig. 3. Pei , Pef are the momenta of the incident

electron prior to and following the reaction, Pai , Paf are the momenta of the target

prior to and following the reaction, ma is the mass of the target, me is the mass

of the electron, Eexc is the excitation energy of the state formed in the collision,

(θe, φ e) are the scattered electron angles (in spherical geometry) and (θa, φ a) are

the target recoil angles. Conservation of energy then requires

E incident = + ai = + + E exc = E final , (1)

2m e 2m a 2m e 2m a

FIG. 3. The general coordinate system in the laboratory frame of reference. The target has an initial

momentum Pai in the x direction and is deflected through to spherical angles (θa, φa ) with a final

momentum Pa f . The electron has initial momentum Pei in the z direction and is scattered to a spherical

angle (θe, φe ) with momentum Pe f .

STUDIES OF ELECTRON-EXCITED TARGETS 169

0 = Pe f sin θe sin φe + Pa f sin θa sin φa (y direction) (2)

Pei = Pe f cos θe + Pa f cos θa (z direction)

the system to the collision. Apart from the condition where the incident electron

energy is very close to the excitation energy of the state Eexc, it can be assumed

that the kinetic energy of the target is much smaller than the kinetic energy of

the electron. It is only in the energy region where the electron kinetic energy is

similar to the incident target kinetic energy that deviations between a complete

dynamical model and the model used here become apparent. This assumption

allows simplification of these equations so that the final target momentum can be

written as

Pa f = Pei2 + Pai2 + Pe2f − 2ζPe f sin(θe + δ),

Pei

where ζ = Pai2 cos2 φe + Pei2 δ = tan−1 ,

Pai cos φe

Pe2f sin2 θe + Pai2 − 2Pai Pe f sin θe cos φe

tan θa = , (3)

Pe f cos θe − Pei

Pe f sin θe sin φe

tan φa = .

Pe f sin θe cos φe − Pai

If a geometry is chosen where the incident and deflected targets are confined to a

plane with φa = φe = 0◦ , Eq. (3) simplifies to

Pa f = Pei2 + Pai2 + Pe2f − 2ξ Pe f sin(θe + ),

Pei

where ξ = Pai2 + Pei2 = tan−1 , (4)

Pai

Pai − Pe f sin θe

tan θa = φa = 0.

Pei − Pe f cos θe

In this planar scattering case, the recoil angle α = (90◦ − θ a) increases as the

initial target momentum decreases. Vector momentum diagrams representing

planar scattering are shown in Fig. 4. For forward electron scattering (Fig. 4a),

170 Andrew James Murray and Peter Hammond

FIG. 4. (a) Forward, (b) backward, and (c) general electron-scattering conditions in planar geometry.

The extremes of forward and backward scattering of the metastable target are shown, together with the

more general case. Two solutions can exist along a given path of the outgoing target such that energy

and momentum are conserved.

momentum transfer to the target results in small recoil angles. For backward elec-

tron scattering (Fig. 4b), large recoil angles result from the collision. However,

in general (Fig. 4c), for any given recoil angle α, two possible values of the out-

going target momentum Paf can exist, each corresponding to a different electron

scattering angle θe.

To illustrate the dual nature of the reaction, and the relationship between the

electron-scattering angle θe and the target recoil angle α, Fig. 5 shows the results

of modeling the collision for an incident electron of energy 40 eV with a helium

target of initial velocity 1960 m/s (this is typical for a supersonically expanded

beam as used at Manchester). The 23S1 metastable helium atom with excitation

energy Eexc = 19.82 eV is assumed to be excited in the reaction, and so the final

energy of the scattered electron is 20.18 eV. The momentum of the target prior to

the collision is therefore known, as is the momentum of the incident and scattered

electron. The final target momentum Paf can then be determined as a function of

electron-scattering angle from θe = 0◦ through to θe = 180◦ using Eq. (4).

In Fig. 5a, the atom deflection angle α is plotted as a function of θ e. Under

these conditions, the atoms recoil through angles from around 4.2◦ for forward

electron scattering through to around 24.8◦ for backward scattering. Figure 5b

illustrates the dual nature of the reaction, where the deflection angle is plotted

as a function of the final target momentum following the collision. At any given

deflection angle between the recoil angle limits, two distinct values of metastable

atom momentum are possible. By experimentally selecting the deflected targets

at a given recoil angle between these limits, the metastable atoms are expected to

travel with two distinct velocities to the detector. By locating the detector a set

STUDIES OF ELECTRON-EXCITED TARGETS 171

FIG. 5. (a) Deflection of helium target traveling at 1960 m/s excited to the 23 S metastable state, as a

function of electron scattering angle for E inc = 40 eV. The atom recoil angles θa and α are shown.

(b) Momentum of helium target traveling at 1960 m/s excited to the 23 S metastable state, for E inc =

40 eV, showing the dual nature of the reaction.

172 Andrew James Murray and Peter Hammond

FIG. 6. Atomic deflection angle as a function of incident electron energy for helium traveling at

1960 m/s.

radius from the interaction region, these velocities transform into different arrival

times for different groups of atoms. Time-of-flight measurements therefore yield

information about the scattering process which produces these different groups.

Figure 6 shows the minimum and maximum deflection angles expected for ex-

citation to specified states of helium as a function of incident electron energy. Near

threshold for excitation of the target state, a reduced angular range is expected.

As the incident energy increases, the range of target deflection angles increases.

Excitation to the metastable states is illustrated, together with excitation to highly

excited Rydberg states which can have lifetimes allowing them to reach the de-

tector before decaying. It is clear that if the target incident momentum is not well

defined, differentiation of atoms excited to specific metastable states is experimen-

tally difficult at incident energies much above threshold. If this condition is not

satisfied, cross sections obtained directly from deflected target yield can only give

information on a mixture of both states. Cascade contributions due to electron

excitation of higher lying states feeding into the metastable states must also be

considered when comparing theory to experiment.

One advantage of measuring the deflected target yield compared to conven-

tional electron-scattering measurements is that a complete set of scattering angles

is accessible, from forward scattering (as measured by Bederson and co-workers)

through to backscattering where θe = 180◦ . In conventional experiments, when

forward-scattering measurements are attempted, the electron detector is often sat-

urated by electrons emitted directly from the electron gun. The backscatter re-

gion is also usually inaccessible, due to the electron source and detector collid-

ing as θe = 180◦ is approached. These regions have therefore remained largely

STUDIES OF ELECTRON-EXCITED TARGETS 173

unexplored using conventional techniques until recently, when a new type of ex-

periment was invented at Manchester. This technique allows both forward and

backscatter regions to be investigated while detecting the electrons, and since this

produces results which can be compared with those obtained from atom recoil

experiments, it is relevant to consider this technique here.

The new method is called the magnetic angle changing technique and was

invented by Frank Read and co-workers in Manchester [43–46]. In these experi-

ments an electron spectrometer is modified to include a pair of current-carrying

coils which straddle the interaction region [43]. These coils produce a magnetic

field localized to the interaction region so that the magnetic field is negligible at

the electron source and the electron detector. By contrast, within the interaction

region the electrons traverse the magnetic field lines and experience a force which

curves their trajectories. The magnetic force deviates the electrons onto velocity-

dependent paths, and so electrons scattered from the target arrive at the detector

at a different angle than that through which they were initially scattered.

It is possible to adjust the magnetic field and detector angle so as to measure

the yield of electrons scattered through all possible angles. Further, since the elas-

tically scattered and direct beam of electrons have different energies from those

inelastically scattered, the inelastically scattered electrons arrive at the detector at

a different angle. Both small- and large-angle inelastic scattering cross sections

can therefore be measured. In addition, by using high-energy-resolution detectors,

the experiments yield cross sections free of cascade contributions. By also using

a high-energy-resolution incident electron beam, different states can be distin-

guished within the resolution of both the detector and source. This resolution is

around 20 meV for the most sophisticated spectrometers operating with a gas-phase

target.

The apparatus developed at Manchester for measuring recoiling metastable tar-

gets is shown schematically in Fig. 7 and is described in detail by Murray and

Hammond [47]. Essential for these experiments is a well-defined target momen-

tum, well-defined incident electron momentum, and a detector with narrow angular

resolution which can rotate accurately around the interaction region. Variations in

these parameters lead to a distribution in the final target momentum and hence a

decrease in experimental accuracy.

A supersonic expansion of the target gas is used to achieve a narrow velocity

spread. The target gas is emitted into a high vacuum from a high-pressure valve

operating with a pressure of 1–2 atm. The gas cools supersonically in the expansion,

and is skimmed by a small exponential skimmer [48] located 150 mm downstream

from the valve. The skimmer/nozzle combination produces an angular spread of 2◦

at the interaction region, constraining the target momentum vector to ±1◦ around

the x axis.

174 Andrew James Murray and Peter Hammond

FIG. 7. Schematic of the experimental apparatus at Manchester. The supersonic gas jet is produced

in the lower source chamber and is skimmed before entering the interaction chamber. An electron gun

provides a well-collimated beam of electrons which interact with the target deflected and detected using

the metastable detector located on a vertical rotating table.

STUDIES OF ELECTRON-EXCITED TARGETS 175

to the Mach number M, which is a characteristic defined by the expansion. The

distribution is given by [49]

3

γ M 2 (v − vs )2

v

f (v) = c exp − , (5)

vs 2vs2

where

kT γ M 2

vs =

m{1 + [(γ − 1)/2] M 2 }

is the stream velocity, T is the temperature of the gas prior to expansion, γ is the

ratio of specific heat capacities (γ = 5/3 for monoatomic gases), c is a constant,

and k is Boltzmann’s constant. The velocity distribution is Gaussian, with an av-

erage velocity given by the stream velocity and a width inversely proportional

to the Mach number. For the helium experiments at Manchester, the Mach num-

ber is around 20, and so the average velocity is ∼1900 m/s with a distribution

of ±6%.

By contrast, the incident electron beam is produced in an electron gun which

has an energy resolution of ∼600 meV [50]. The electron gun is of a two-stage

electrostatic design, and produces a beam with a pencil angle of 2◦ and zero

beam angle at the interaction region. At 40-eV incident energy, the momentum

distribution of the incident electron beam is 3.4 × 10−24 kg m/s with a variation

of ±0.6%. This distribution can be neglected when compared to the much larger

variation in the target beam momentum.

The distribution of momenta in the target beam produces a corresponding un-

certainty in the metastable recoil angle which transforms into an uncertainty in the

corresponding electron-scattering angle. Using a Mach number of 20, the uncer-

tainty in the electron-scattering angle is found to be σ (θ e) ≈ ±3.5◦ for small recoil

angles, whereas this increases to σ (θe) = ±15◦ for a recoil angle α = 23◦ . The accu-

racy of differential cross sections measured using the target deflection technique is

therefore sensitive to the expansion, with higher Mach numbers yielding narrower

velocity profiles and hence greater accuracy.

The supersonic expansion occurs in the source chamber which is pumped by a

2500-liter/s diffusion pump. The pulsed Lasertechnics nozzle [51] opens a piezo-

electrically coupled Viton knife edge seal to release gas into the vacuum chamber

at a repetition rate of up to 150 Hz. The nozzle is driven by a 200- to 500-μs

pulse which can be varied from 10 to 100 V. It is necessary to adjust these driving

parameters to minimize extraneous bounce of the nozzle following initial opening

of the valve, as this decreases the load on the pumping system. By judicious

control of these parameters, the supersonic expansion can be adjusted for maximum

throughput while minimizing the velocity distribution of the beam.

176 Andrew James Murray and Peter Hammond

the interaction chamber using an exponential skimmer with a 1-mm-diameter

orifice [48]. The skimmer is constructed of rhodium-plated copper with a wall

thickness at the orifice of less than 10 μm. This very thin edge ensures that the

gas entering the interaction chamber suffers minimal deflection due to scattering

from the edge of the skimmer. Upon entering the interaction chamber, the gas

travels approximately 150 mm before interacting with a pulsed beam of electrons

emitted from the electron gun. The electron beam interacts orthogonally with the

gas beam, and a Faraday cup placed opposite to the gun monitors the yield of

emitted electrons.

Targets excited and deflected by the interaction are selected using a detector

located on a vertical rotating table which can be moved under computer control

with an accuracy of ± 0.01◦ . The angle of the detector is measured using an

opto-coupled array of LEDs and phototransistors, and the angle is calibrated using

apertured visible laser diodes located in the pulsed nozzle source, vertical table

rotation axis, and electron gun. The metastable target detector is constructed of

310-grade stainless steel, and has a conical input skimmer with a 1-mm entrance

orifice. A second 1-mm aperture located 70 mm behind the input aperture defines

the acceptance angle of the detector. Metastable targets which pass through both

apertures drift a further 100 mm before striking the front cone of a channel electron

multiplier. The resulting current pulse from the CEM is detected, amplified, and

fed to counting and noise-discriminating electronics external to the system.

The interaction chamber is constructed of nonmagnetic 310-grade stainless steel

and is internally lined with a double layer of μ-metal to reduce external magnetic

fields to less than 5 mG. All components inside the chamber are constructed of

nonmagnetic materials including 310-grade stainless steel, advance (constantan)

sheet, aluminum, copper, and PTFE. A full description of the apparatus can be

found in [47].

A time-of-flight measurement of the selected targets determines their momen-

tum following excitation. To facilitate this, the experiment is pulsed at a rate

between 100 and 150 Hz. Once the angle of the detector is adjusted, the experi-

mental cycle commences by opening the nozzle, releasing high-pressure gas into

the source chamber, where it cools supersonically. The edge of the nozzle driv-

ing pulse also starts a multichannel scaler. Helium takes around 300 μs after the

nozzle is opened for the maximum density of the target beam to pass through

the interaction region, and at this time the electron gun is turned on for 4 μs.

The electron beam interacts with the gas which is deflected. A small, angularly

resolved sample of deflected targets is selected by the analyzer, and these are

detected by the channel electron multiplier. The CEM pulse is amplified and dis-

criminated against noise before being fed to the multichannel scaler, where it is

recorded.

The experiment is repeated many times to accumulate a time-of-flight spectrum.

After a preset number of nozzle pulses, the resulting time-of-flight spectrum is

STUDIES OF ELECTRON-EXCITED TARGETS 177

recorded, the analyzer moves to a new detection angle, and the sequence is repeated

until a complete set of results is obtained over all recoil angles. The time-of-flight

spectrum yields the speed of the atoms (and hence the magnitude of their momen-

tum), since the detector rotates at a constant radius around the interaction region.

Figure 8 shows examples of time-of-flight spectra obtained from the manifold of

21,3S metastable states of helium. The incident electron energy was 40 eV, and the

signal accumulated for 250,000 nozzle pulses at each detection angle. The dual

nature of the detected signal can be seen. Two Gaussian peaks are fitted to the data,

allowing the signal under each peak to be determined. This relates directly to the

probability of excitation of the metastable atoms, allowing the differential cross

section to be established.

To estimate this cross section, time-of-flight spectra were accumulated at 1◦

intervals from α = 4◦ through to α = 28◦ . Figure 9 shows the result of these mea-

surements, where the peak amplitude, position, and width are plotted as functions

of detector angle. At lower and higher deflection angles the peaks are difficult to

distinguish, and so there is an increased uncertainty in the measurements at these

angles. The dual nature of the result is seen in Fig. 9b, and compares favourably

with the prediction of Fig. 5b.

The differential cross section (DCS) for electron excitation of a target can be

written as

dσ

DCS = (6)

d

where d is the solid angle at spherical angles (θe, φ e) with respect to the incident

beam direction. Since the experiments measure the excited target yield, it is neces-

sary to relate the target momentum to the correlated electron-scattering direction.

This is accomplished by rearranging Eq. (4) :

−1 Pai − Pa f sin θa

θe = tan (7)

Pei − Pa f cos θa

m a xint

Pa f = (8)

tint

where ma is the mass of the target and xint is the distance from the interaction region

to the detector; tint is the time the atom takes to reach the detector from the interac-

tion region obtained from Fig. 9. The values of Pai and Pei were calculated by fitting

Eq. (4) to the data of Fig. 9b using a least-squares fit. The calculated incident energy

FIG. 8. Selected examples of the time-of-flight spectrum from helium with E inc ≈ 40 eV. For details, see text.

STUDIES OF ELECTRON-EXCITED TARGETS 179

FIG. 9. Data obtained from fitting Gaussian peaks to the time-of-flight spectra obtained when

exciting helium at around 40 eV incident electron energy. Part (a) shows the fitted peak heights and

Part (c) the associated widths. Part (b) indicates the peak time of arrival from opening the gas nozzle.

The dual nature of the deflection process can be seen.

of the electron beam was 40.8 eV, and the momentum of the incident target beam

was found to be Pai = 1.3 × 10−23 kg m/s, corresponding to a speed of 1960 m/s.

The relative magnitude of the differential cross section is given by the area under the

Gaussian peaks fitted to the data, and this relates directly to the relative differential

cross section measured using conventional electron spectrometers.

180 Andrew James Murray and Peter Hammond

FIG. 10. (a) DCS measurements exciting the 23,1 S and 23 P states of helium for an incident electron

energy of 40 eV using the magnetic angle changing technique of Ref. [46]. The results from θe = 0◦

to θe = 180◦ are normalized to the CCC calculations of Ref. [53]. (b). Estimated relative DCS for

excitation to the 23,1 S metastable states of helium for an incident electron energy of 40.8 eV obtained

from the measurements in Fig. 9. Also shown are the summed differential cross sections from excitation

of the 23,1 S metastable states and 23 P states of helium shown in Fig. 10a.

troscopy and the recoil atom technique is shown in Fig. 10. The results of Cubric

et al. [46] using the magnetic angle changing technique are shown in Fig. 10a, the

results being placed on an absolute scale by normalizing to the convergent close

coupled (CCC) calculation of Fursa and Bray [53]. The singlet cross section is

seen to be dominant for forward scattering, with a deep minimum at scattering

angles θ e ≈ 50◦ . The 23P cross section is reasonably uniform across all scatter-

ing angles, whereas the 23S cross section varies by a factor of ∼60 as the scattering

angle is varied.

STUDIES OF ELECTRON-EXCITED TARGETS 181

Figure 10b shows the measured DCS obtained from the recoil measurements

of Fig. 9. The cross section is forward peaked, with a minimum around θ e = 90◦ .

The uncertainty in the deduced electron-scattering angle is obtained from the peak

width, which is directly proportional to the variation in velocity of the incident

target beam. The calculation does not consider effects due to noncoplanar contri-

butions (i.e., when φ = 0◦ ), but a more detailed study indicates that these effects

are small for the acceptance angle of the detector and at this energy. Noncoplanar

contributions must be considered when the incident energy is close to threshold for

excitation of the state, and when the detector solid angle is significantly widened

to increase yield.

Cascades from higher-lying states which feed the metastable states produce

additional contributions to the yield. These contributions depend on the differential

cross section for excitation of these higher states, together with the branching ratio

for decay back to the metastable state. It has been estimated [52,54] that cascade

contributions to the 21S0 metastable state play only a minor role, since most higher

lying singlet states decay preferentially to the 11S0 ground state. By contrast, all

upper triplet states decay to the 23S1 metastable state and so there is significant

contribution from these decay routes. Harries [52] used the data of Cubric et al.

[46] and Trajmar et al. [54] to estimate this contribution by assuming that the

excitation cross section for the n3L series is proportional to n ∗−3 , where n ∗ = n−δ l

and δ l is the associated quantum defect. This analysis (which did not include

angular contributions) indicates that up to 80% of the measured 23S1 yield is due

to cascade contributions at this energy.

To establish a comparison between the recoil cross-section results and those

using the magnetic angle changing technique, it is assumed that all singlet states

apart from the 21S0 state decay directly to the ground state. Further, it is assumed

that the only triplet states significantly excited at this energy are the 23S1 and 23P

manifold. Figure 10a shows the measured cross sections for excitation of each of

these states, and so it is possible to sum these results to predict the cross section

for the manifold of metastable targets.

Figure 10b also shows the result of summing these contributions and compares

this with the results from the recoil measurements. An arbitrary normalization

has been chosen to yield best overall agreement, since the recoil data are not

measured on an absolute scale. The recoil data are seen to compare well with

the summed signal from [46]. The major contribution to the cross section in the

forward direction arises from the 21S0 state, whereas at intermediate scattering

angles, from θ e = 30◦ to θ e = 100◦ , cascade contributions from the 23P states

dominate. At higher scattering angles the singlet state once more dominates, until

at θ e = 180◦ the 21S0 and 23S1 states have equal probability of excitation, with

cascade from the 23P states providing only a small contribution. These results

indicate that the approximations regarding the cascade contributions discussed

above are reasonable.

182 Andrew James Murray and Peter Hammond

Although the recoil atom measurements agree well with the electron-scattering

measurements, the technique is restricted because the spectrometer can resolve

neither the cascade contribution nor the individual metastable state contribution

excited by electron impact. The recoil technique is therefore most applicable

when the states are widely spaced in energy, and this is discussed further in

Sect. III. For targets with closely lying states, the results are difficult to inter-

pret since many different states contribute. A different method is therefore re-

quired to study these interactions. Section IV describes such a technique, where

a high-resolution laser probes individual states within the metastable manifold.

These experiments produce results of far greater detail than is possible using con-

ventional electron-scattering experiments, and have the potential to provide new

information on electron-impact excitation of many different molecular and atomic

species.

Decay Product: Recoiling Excited Atoms

A. PRINCIPLES

In Sect. II the kinematics of interactions between electrons and targets which pro-

duce metastable excited targets was outlined. The yield of metastable targets as a

function of recoil angle and time-of-flight was explored in the laboratory frame,

and experimental results confirming the predicted distributions were shown. In

this section a method is described in which the angular and time-of-flight distribu-

tions are utilized to enable observation of targets excited to doubly excited states

which decay by fluorescence. The results demonstrate that doubly excited targets

can be observed without the continuum background signal which has plagued

observations for decades.

In previous studies, doubly excited targets formed in electron-impact experi-

ments have been difficult to study for three principle reasons: (1) excitation cross

sections are small in comparison to singly excited state cross sections; (2) signal

relating to doubly excited states is almost invariably embedded in the continuum

with which interference occurs; and (3) doubly excited states lie in an excitation

energy region which also contains triply excited negative ion states with which

they can be confused. The majority of previous work has involved detection of

either the scattered electron, the ejected electron, or the positive ion arising from

the excitation and autoionizing decay of the doubly excited states. The earliest

such electron-impact experiments [55–59] reported observations of the (2s2)1S,

(2s2p)3P, and (2p2)1D states in helium, which are optically forbidden in excitation

from the ground state but which can autoionize. These measurements comple-

mented photoabsorption measurements of Madden and Codling [60], who reported

the first observation of doubly excited states. All of these techniques are particularly

sensitive to the energetically broad doubly excited states that can autoionize.

STUDIES OF ELECTRON-EXCITED TARGETS 183

For doubly excited states that cannot autoionize, experiments have to be directed

toward the scattered electron or to the decay products. Burrow [61] reported the

observation of the (2p2)3P state which is stable against autoionization, with a

total cross section of 4.4 × 10−21 cm2 at 0.11 eV above threshold. Fluorescence

measurements of the (2p2)3P state [62], made by observing the XUV radiation at

32 nm arising from the transition (2p2)3P to (1s2p)3P [63], enabled the observation

of the decay of highly excited negative-ion states via autodetachment into the

(2p2)3P state. A subsequent experiment [64] queried Burrow’s identification of the

(2p2)3P state.

Metastable singly excited atoms are also produced in the decay by fluorescence

of doubly excited atoms. Shpenik and co-workers [65] reported observations of

electron-impact-formed doubly excited states in helium using the metastable atom

recoil technique in which the yield of metastable atoms as a function of incident

electron energy and atom recoil were recorded. The doubly excited states were

observed as interference profiles with, and dominated by, the very large yield of

directly excited metastable atoms. In other experiments the decay of triply excited

negative-ion states has been observed by autodetachment to metastable states.

Defrance et al. [32] used the technique described in Sect. II, measuring metastable

atom recoil as a function of incident electron energy, atom scattering angle,

and metastable atom time of flight to perform a measurement of the (2s22p)2P

negative-ion state of helium. Trantham et al. [66] explored the structure of the

negative-ion states using both metastable atom yield and electron spectroscopy.

In other inert gas targets, the metastable atom yield has been used to study highly

excited states [25, 67].

In photoexcitation studies the observation of doubly excited states in helium

via photon and metastable atoms as fluorescence decay products has been pi-

oneered by Hammond and co-workers [68–70]. The use of the radiative decay

route was shown to provide excellent sensitivity to the energetically narrow dou-

bly excited states without the presence of a continuum background signal. Related

high-energy-resolution experiments have explored the branching ratio between the

autoionization and fluorescence decay routes [71–73]. These experiments provided

the motivation for extending electron-impact studies using metastable atom recoil

spectroscopy.

The primary goal of these new experiments is to distinguish between singly

excited metastable atoms formed by direct excitation and singly excited metastable

atoms formed by fluorescence from doubly excited states [74]. It is also desirable

to isolate the doubly excited state signal from that arising from triply excited

negative-ion states.

The principle underlying these experiments is as follows. The momentum trans-

ferred to a target excited by electron collision is represented by Fig. 4c. The mo-

menta of the metastable atoms, measurable with the apparatus described, fall on

the upper dashed circle shown in this figure. For excitation near threshold where

Pef is small, the circle is of small diameter. As the impact energy increases, Pef

184 Andrew James Murray and Peter Hammond

increases and so the diameter of the circle also increases. When the incident elec-

tron energy is just sufficient to excite a doubly excited state, the end points of the

final momenta Paf of the doubly excited atoms are therefore represented as lying

on a small-diameter circle. However, at the same incident electron energy it is also

possible to form singly excited atoms with final momenta represented by a second,

larger-diameter circle which encloses that describing the doubly excited atoms. The

momentum change of the atom following emission of a photon in the fluorescent

decay process is negligible, so that the metastable atom decay product retains the

final momentum signature of the doubly excited atom from which it forms. Thus,

in general, at atom recoil angles that intersect both circles, four well-defined mo-

menta exist. The lowest and highest momenta are from directly excited metastable

atoms, and the two intermediate momenta are from the doubly-excited-state decay

product. It is therefore possible to separate the metastable atoms arising from the

two different formation processes.

B. EXPERIMENTAL TECHNIQUES

The apparatus described in Sect. II provides the means to study the metastable

product of the decay by fluorescence of doubly excited states. A metastable atom

detector with a wide acceptance angle replaces the detector described in Sect. II.

This new detector is placed closer to the interaction region and has a larger entrance

to provide a wider acceptance angle. Between the entrance aperture and the channel

electron multiplier a series of biased open aperture plates [69, 70] prevent scattered

electrons and positive ions from striking the CEM. The increase in detection solid

angle is necessary because the yield of metastable atoms from this decay is very

low. This detector also provides excellent sensitivity at threshold, since it can

detect a broader range of atoms with contributions also from events out of the

scattering plane.

FLUORESCENCE DECAY PRODUCTS

Demonstration [52, 74] of the separation of metastable atoms arising from

decay by fluorescence of doubly excited states from those directly excited is shown

in Fig. 11, where the yield of metastable atoms arising from electron impact at

63.3 eV is plotted as a function of atom scattering angle and time of flight. The

large-diameter oval structure which dominates the data represents the direct exci-

tation processes. The low-intensity structure lying within this oval at 21◦ and 58 μs

represent metastable atoms arising from the decay of doubly excited states. These

data compare well with the results shown in Fig. 5b, where the signal arising from

the decay of doubly excited states appears as a second, smaller oval lying within

that due to directly excited atoms.

STUDIES OF ELECTRON-EXCITED TARGETS 185

FIG. 11. Time of flight of metastable helium atoms as a function of atom recoil angle at an incident

electron energy of 63.3 eV. The oval structure represents detection of directly excited metastable atoms.

The structure centered at 21◦ and 58 μs represents atoms arising from fluorescence decay of doubly

excited states. A logarithmic gray scale represents yield.

The yield of metastable helium atoms can also be measured at a given recoil

angle as a function of incident electron energy and time of flight. The data, shown

in Fig. 12, can be divided into two distinct regions. In the first region, metastable

atoms arising from directly excited states lie in two bands at approximately 45 and

72 μs, corresponding to electron scattering angles of 120◦ and 70◦, respectively. The

second region lies between these bands and represents metastable atoms arising

from fluorescence decay of doubly excited states. This region changes rapidly as

the incident energy increases from 60 to 65 eV. At 80 eV the structure becomes

two bands at approximately 52 and 67 μs, corresponding to electron-scattering

angles of 100◦ and 60◦ , respectively.

Doubly excited state excitation functions can be extracted from the two-

dimensional time-of-flight data in Fig. 12. This is achieved by summing the

yield lying between the dominant fast and slow metastable atom yields. The re-

sults of this summation are shown in Fig. 13. Signal arising from doubly excited

atom decay is clearly apparent in the region below the He+ (N = 2) ionization

threshold. No similar structure can be observed below higher ionization thresh-

olds, in marked contrast to the photoexcitation results of Sokell et al. [68]. The

structure lying below the He+ (N = 2) ionization threshold represents doubly ex-

cited states that decay by fluorescence. The states that can appear here are states

186 Andrew James Murray and Peter Hammond

FIG. 12. Time of flight of metastable atoms as a function of incident electron energy at an atom

recoil angle of 20◦ . Metastable atoms arising from fluorescence decay of doubly excited states lie in

the 50- to 63-μs region of the spectrum. A logarithmic gray scale is used to represent yield.

FIG. 13. Doubly excited state excitation function extracted from the time-of-flight spectrum shown

in Fig. 12. The excitation energies of known doubly excited states are marked.

STUDIES OF ELECTRON-EXCITED TARGETS 187

that are either parity favored or unfavored to autoionize. It is likely that states with

a lower probability to autoionize will be more likely to fluoresce. However, the

energy resolution used in these measurements is insufficient to allow individual

states to be identified. The residual yield of directly excited metastable atoms

results in an underlying background which decreases as the electron-impact energy

increases.

This new capability to resolve the metastable decay product of doubly excited

states allows these states to be studied free from a large continuum background and

without the complication due to interference. In addition, triply excited negative-

ion states that autodetach to produce singly excited neutral atoms [32, 66] can-

not be distinguished from directly excited atoms and so are separated from the

decay product of doubly excited atoms in momentum space. Only triply excited

negative-ion states that autodetach into doubly excited states and that subsequently

fluoresce can contribute to the yield detected here. At present the technique can

be used for light targets where the momentum definition of the incident beam

allows sufficient angular and temporal separation of the recoiling targets. In the

future, laser cooling which produces a well-defined momentum will enable de-

tailed measurements of doubly excited states to be conducted for a wide range of

targets.

A. PRINCIPLES

Sections II and III show how differential cross sections can be extracted from

the deflected target yield following electron impact. Section II describes how

this is applied to direct excitation processes, whereas Sect. III indicates how

the technique can be applied to investigate doubly excited states. In both cases,

cascade contributions play a role. For direct excitation, these contributions reduce

the information which can be obtained, whereas for doubly excited states cascade

contributions are exploited to provide information about these states.

It is of interest to maximize the information obtained from an experiment, and

so it is beneficial to consider more sophisticated methods that allow extraction of

additional information. The technique adopted at Manchester uses stepwise laser

excitation to probe metastable targets following electron excitation. This allows

details to be obtained about closely lying states within the metastable manifold,

since the high spectral resolution of the laser is exploited. The combined electron-

impact and laser excitation techniques provide details about the reaction which

would be impossible to obtain using either technique separately.

The stepwise excitation scheme adopted is shown in Fig. 14. The incident

electron scatters from the reaction, deflecting and exciting the target. The target

188 Andrew James Murray and Peter Hammond

between these states. Properties of the upper state are then measured, either by

observing the fluorescence from the laser excited state or by field ionizing the

target and detecting the resulting ions.

Since the laser radiation transfers information from the electron-excited state

to the upper state in a controlled way, this information can be extracted. A further

advantage is that the laser has very high spectral resolution (typically μeV to neV).

Hence, by varying the laser wavelength, different states within the metastable

manifold can be analyzed. This resolution is a factor of 103–108 better than is

possible with even the most sophisticated electron spectrometers.

The stepwise excitation scheme has been exploited in a number of different

ways, principle among these being the observation of fluorescence from the laser-

excited target. This has been used to evaluate partial differential cross sections

for both metastable and nonmetastable atoms excited by electron impact. This is

achieved by observing the polarization of the emitted fluorescence from the laser-

excited state [75–77]. Such experiments are often performed close to threshold so

that cascade contributions are eliminated.

An example of this technique was the first test of the Percival–Seaton hypothesis,

which predicts that the nuclear spin does not play a role when a target is excited by

electron impact [78, 79]. In these experiments a continuous-wave (CW), tunable,

single-mode ring dye laser resonantly excited the 61P state of mercury to the 61D

state from which fluorescence was monitored. The laser had sufficient resolution

to isolate individual isotopes, a technique impossible by other means. The partial

differential cross sections were measured as a function of incident energy for

STUDIES OF ELECTRON-EXCITED TARGETS 189

isotopes with different nuclear spins. The Percival-Seaton hypothesis was found

to be valid at higher incident energies, but was found to break down as threshold

was approached.

A more sophisticated experiment has been performed by the Griffith group

[80–85], who measured the polarization of light emitted from the laser-excited state

in coincidence with the scattered electron. A well-defined beam of electrons excited

mercury to the 61P1 state and the scattered electron momentum was determined

using a cylindrical electron analyzer. The target was illuminated with radiation

from a stabilized CW ring dye laser operating around 579 nm, which excited

the target from the 61P1 state to the 61D2 state. The wavelength was chosen to

excite only the I = 0 isotope, thereby eliminating spectroscopic contributions

from other isotopes. The laser polarization was also varied, allowing a complete

set of scattering parameters (ρ 00, L ⊥ , Plin, and γ ) to be evaluated for the 61P1 state

without the need to measure the in-plane P4 Stokes parameter [86].

Stepwise techniques have also been used to study highly excited Rydberg atoms.

These atoms can be produced using one or more lasers tuned to excite the target to

high principal quantum numbers. Using high-resolution laser techniques, atoms

with principal quantum numbers greater than 300 have been produced [87]. The

highly excited electrons in these atoms behave as quasi-free particles when far

from the nucleus, and so experiments can be performed which use these electrons

for very-low-energy scattering experiments from other targets [88].

If an electric field is applied during the laser excitation process, it is possible to

Stark mix states of high n to produce atoms with high angular quantum numbers.

These “planetary” atoms have very long lifetimes, since the electrons spend most

of their time far from the nucleus. Planetary atoms are extremely sensitive to

small external perturbations which promote ionization. Since ions produced by

these perturbations can be detected with high efficiency, these targets have been

proposed as sensitive probes of low-intensity infrared radiation for astronomical

applications [89].

Whereas it is usual to observe the fluorescence in stepwise experiments, this can

have disadvantages since the fluorescent photon may not be emitted in the direction

of the detector. In addition, detectors may not be available that are sensitive to the

emitted radiation. This problem increases for coincidence studies, since both the

electron and the photon from a correlated scattering event must enter the detectors

simultaneously to register a true coincidence. The resulting coincidence yield is

therefore low, and long accumulation times are required.

An alternative detection method is to laser-excite the target to a high Rydberg

state which is then field ionized, the resulting ion being detected. The advantage of

this technique is that field ionization is efficient, and it is possible to collect all ions

that are produced. A disadvantage is that laser excitation to the Rydberg states is not

efficient, the probability of excitation being proportional to laser power density.

190 Andrew James Murray and Peter Hammond

A tunable high-power pulsed laser is usually required, which has much lower

spectral resolution compared to the CW ring lasers described above. The repetition

rate of these lasers is also low, and so the experiment must be operated in a

pulsed mode with the target source, electron gun, laser, detector, and electronics

all being pulsed. The apparatus described in Sect. II is designed for these types of

experiments.

B. EXPERIMENTAL TECHNIQUES

To implement these experiments, the apparatus described in Fig. 7 is modified

to include a field ionization detector which encompasses the interaction region.

The upper rotating detector is also modified to include a field ionization detector,

allowing momentum selected targets to be probed by the laser while simultaneously

monitoring the metastable yield. A laser which produces a high-power laser beam

is needed, and this is provided by a YAG pumped doubled dye laser.

Figure 15 depicts the laser system used at Manchester. A YAG laser operating at

532 nm is Q-switched at 20 Hz using an external high-stability crystal-controlled

clock [89]. The YAG laser pumps a dye laser, the oscillator being pumped by 3% of

the input light and the amplifier by 97% of this radiation. A diffraction grating in the

oscillator cavity selects the laser wavelength. When radiation from the oscillator

passes through the amplifier cell, stimulated emission produces a bright pulse of

radiation with a peak power around 3 MW. The dye laser radiation is doubled to

produce a UV beam with a peak power around 100 kW and a temporal width

of ∼5 ns.

FIG. 15. The laser system that produces tunable pulsed radiation for the stepwise experiments.

STUDIES OF ELECTRON-EXCITED TARGETS 191

The UV laser radiation is directed inside the vacuum system using optical fiber.

This has the advantage that the laser beam can be focused onto the interaction

region while the system is open. Upon closing the vacuum system, it is only

necessary to couple the laser radiation into the fiber for the beam to illuminate the

interaction region. The electron gun and Faraday cup are also shown in Fig. 15, and

it can be seen that the laser–target interaction region is displaced from the electron–

target interaction region. The field ionization plates for the lower detector which

encompass the interaction regions are also illustrated.

The laser–target and electron–target interaction regions are displaced, as this

allows highly excited or ionized atoms created by electron impact to be eliminated

from the field ionization signal. Measurements can then be conducted for electron-

impact energies above the ionization threshold, where the large yield of ions created

directly by electron impact would swamp the stepwise laser signal if the two

interaction regions were coincident.

The EHT electrode of the field ionization detector is pulsed up to a maximum of

3 kV to field ionize the laser-excited targets. Ions which are created accelerate onto

the entrance of an ETP electron multiplier [20], and the output pulse is amplified

and directed to external counting electronics. The ion signal is monitored as a

function of laser wavelength and electron-impact energy [50, 47].

The electronic hardware needed to control these interactions is more com-

plex than described in Sect. II, since the timing is critical in these experiments.

Overall timing is governed by a custom-built delay generator [89] which can be

programmed manually or via a PC. The repetition rate of the experiment is dic-

tated by the 20-Hz maximum rate at which the laser can be operated. As before,

the timing sequence is initiated by opening the target gas nozzle. For helium, the

laser flashlamps are fired 150 μs after the nozzle is opened, in preparation for

Q-switching the YAG laser. Around 300 μs after the nozzle is opened, the peak

of the helium beam arrives at the electron–target interaction region. The electron

gun is then turned on for 4 μs and metastable targets are excited. Since highly

excited Rydberg atoms and ions may also be created, the field ionization plates

are fired 40 ns after the electron gun is switched off using an EHT pulse switched

on for 1 μs. This removes ions and Rydberg atoms from the gas beam, allowing

only metastable and ground state targets to drift to the laser–target interaction

region.

Metastable helium atoms take around 10 μs to drift to the laser–target interaction

region following the electron gun pulse, and at this time the laser Pockel cell is

triggered, initiating a laser pulse. Laser radiation resonantly excites the metastable

targets to high Rydberg states. At 50 ns after the laser is initiated, the EHT pulse

is fired for 2 μs and the laser-excited targets are field ionized and accelerated to

the detector. The detector signal is gated before being passed to a constant fraction

discriminator which feeds a timer counter. The signal is then recorded by the

computer.

192 Andrew James Murray and Peter Hammond

The metastable signal detected by the upper detector (Fig. 7) is monitored during

the interaction, as this allows the electron beam to be focused and steered onto

the gas target beam. Prior to carrying out these measurements the upper and lower

detectors are rotated to the desired target recoil angle using the stepper motor

electronics controlled by the computer.

Stepwise experiments using the lower field ionization detector do not produce

differential cross sections, since there is no angle discrimination of the recoiling

targets. This detector therefore produces an integrated cross section, with a corre-

sponding high yield. To measure differential cross sections for metastable targets

probed by the laser it is necessary to laser excite and field ionize targets selected

by the upper detector. Field ionization plates are therefore also located in this de-

tector, and the fiber-optic coupler is relocated to illuminate atoms selected by this

detector [47, 50]. The yield of laser-excited field-ionized targets is low in these

experiments, and so long accumulation times are required.

The timing sequence for stepwise experiments in the upper detector is identical

to that for the lower detector, except that the laser pulse and second field ionization

pulse are delayed until the targets drift into the laser–target interaction region inside

the upper detector. For helium, this occurs around 100 μs after the electron beam

pulse is initiated. Since the laser selects individual states within the metastable

manifold, differential cross-section measurements for excitation of these states

can be determined.

Stepwise experiments can be carried out in the lower detector, where there is no

angular selectivity of the excited targets and the yield is high, or in the upper

detector, where the excited targets are angle selected prior to laser excitation, with

a corresponding lower yield. Results from both of these detectors are described in

this section.

The atomic target which is easiest to study is helium, since this is the lightest

atom which can be produced in a supersonic expansion. Rydberg states with prin-

cipal quantum numbers from n = 20 to n = 80 can be accessed from the 21S0

state using the dye laser described above. Resonant laser radiation is produced by

doubling the light from the dye laser operating between 626 and 630 nm.

Figure 16 shows a typical spectrum obtained using the lower detector. The laser

excites the electron-impact-excited metastable 21S0 atom to the n1P1 state. Ions

are detected by field ionization from the n = 21 through to the n = 60 states in

this example. The spectrum was obtained by firing the laser 100 times for each

recorded channel of the spectrum. The incident energy of the electrons was 22 eV,

and the average beam current was 740 pA. A 1000-V, 2-μs field ionization pulse

was fired 50 ns after the laser beam passed through the metastable beam, and the

average UV laser power density was 10 mW into a 1-mm2 beam. For n = 30, an

STUDIES OF ELECTRON-EXCITED TARGETS 193

FIG. 16. High Rydberg spectrum obtained by resonantly exciting the 21 S0 state to the n 1 P1 state,

with n = 21 to n = 60. The laser wavelength is plotted on the x axis.

average of 3.5 ions were detected for each laser pulse, indicating the efficiency of

the detection process in these experiments.

The variation in the observed intensity shown in the figure is due to a number

of factors, including the laser excitation efficiency, laser intensity profile, field

ionization efficiency, and detector efficiency. Since the ions are all created with

almost identical kinetic energy following field ionization, the detector efficiency

remains constant as the spectrum accumulates. The ETP detector efficiency peaks

for ions accelerated to ∼10 keV, but in these experiments the anode was set to

2.5 kV and so the ion energy at the detector was around 3 keV. The ETP detec-

tor was therefore not operating at maximum efficiency when these results were

obtained.

The efficiency of laser excitation of the Rydberg state depends on a number

of factors, including the absorption and stimulated emission characteristics of

the laser–atom interaction together with the radial overlap integral between the

21S0 and n1P1 states. The laser–atom interaction can be modeled since the high

Rydberg states are hydrogenic in nature, with corresponding well-defined wave-

functions [90]. These models indicate that the laser excitation probability decreases

as n → ∞. By contrast, the field ionization efficiency increases as n increases. This

process therefore partly compensates for the decrease in efficiency due to the laser

interaction, allowing higher-n states to be detected. Correspondingly, the low yield

when n decreases toward n = 21 is due to the lower probability of field ionization

from these deeper-lying states.

One striking feature in this spectrum is the absence of ions created when the

laser is off-resonance. The signal-to-noise ratio is therefore very high. This is

important for stepwise experiments carried out in the upper detector, where the

194 Andrew James Murray and Peter Hammond

density of metastable targets is low, since it is the high signal-to-noise ratio that

allows the field-ionized signal to be measured in this detector.

The excitation energy of the states shown in Fig. 16 follows the regular n−2

energy dependence which can be derived from the Rydberg formula. This is ex-

pected for helium, as LS coupling is strictly observed, and the states are well

separated in energy. Helium therefore provides a test bed to calibrate the appa-

ratus, and is used extensively throughout the experimental program to check the

operation of the instrument.

By contrast, Fig. 17 shows the spectrum obtained using argon as a target with

laser radiation around 295 nm. In this study the incident electron energy was

14 eV, the atom being excited from the ground state to metastable states with

excitation energies around 11.6 eV. Argon has two ionization limits, depending on

the coupling of the valence electron to the ionic core. The 2P3/2 core ionization

limit is at 15.73 eV, whereas the 2P1/2 core limit is at 15.91 eV.

Moore [91] indicates that jl coupling is required to describe the states

of argon, and this coupling scheme is adopted here. The electron-excited

metastable state accessed by the laser is the (nominal) 3P2 state at 11.52 eV,

which is designated as 4s[3/2]0J =2 in jl coupling. The laser radiation resonantly

couples this state to higher-lying states with selection rules being restricted

to J, K = 0, ±1. Rydberg states that can be resonantly excited are there-

fore the np[3/2] J =2,1, np[5/2] J =3,2, np[1/2] J =1, np ′ [3/2] J =2,1, np ′ [1/2] J =1,

n f [3/2] J =2,1, n f [5/2] J =3,2 , and n f ′ [5/2] J =3,2 states, where the prime indicates

the 2P3/2 ionic core has changed to the 2P1/2 core during the transition.

Figure 17 shows the Rydberg series observed in argon, again using the lower

field ionization detector. The assignments are due to Pellarin et al. [92] who used

a multichannel quantum defect theory to determine the energies of the Rydberg

states in this region. Dominant in the spectrum are transitions to the 10p′ [3/2] J =2

and 10p′ [1/2] J =1 core changing states. These are the most energetic 2P1/2 core

states which lie below the first ionization limit, and so these can be field ionized

and detected. The strength of these transitions is due to the large overlap between

the metastable state wavefunction and the n = 10 state wavefunctions compared to

the corresponding overlap with states of n > 29.

The argon spectrum illustrates the difficulty of resolving individual high

Rydberg states using the pulsed dye laser. Pellarin et al. [92] measured their spec-

trum using a CW dye laser, easily resolving individual states up to n = 70. This was

possible because the resolution of the CW laser was around 100 neV, in contrast to

the resolution of the pulsed dye laser, which is around 20 μeV. The pulsed system

has the advantage that the signal is more intense than that obtained using a CW

source, but the resolution of the pulsed laser restricts the experiment to probe states

whose energy difference is larger that this. These limitations are further discussed

in Sect. V.

Restrictions due to energy resolution are compounded when studying molecular

targets, since for each electronic transition in a molecule there is an associated

FIG. 17. High Rydberg spectrum obtained by resonantly exciting from the 33 P2 state of argon to high Rydberg states. The laser

wavelength is plotted on the x axis. Transition assignments are due to Pellarin et al. (1988) [Ref. 92].

196 Andrew James Murray and Peter Hammond

*

u metastable state manifold by resonant

laser radiation between 350 and 365 nm.

rotational and vibrational series due to the motion of the atoms around their center

of mass. Direct electron-impact excitation studies of molecules are restricted by

the resolution of the spectrometer, which is at best around 20 meV. It has been

impossible to resolve individual rotational states for any molecular species other

than H2, and only a limited number of targets have vibrational energy spacings

large enough to be resolved directly using electron impact [93].

These difficulties can be resolved using stepwise laser techniques, since it is

possible to access individual vibrational and rotational states created by electron

impact. Experiments conducted so far with the techniques described here have

been from the c3u metastable states of hydrogen, although a preliminary study

of nitrogen has also been carried out.

One complication with these studies is the diversity of high Rydberg states which

can be accessed. Fig. 18 is an example of a small portion of the field ionization

spectrum obtained from H2 with the laser tuned between 350 and 365 nm, showing

the complexity of the spectrum to be analyzed. Harries [52] has calculated this

spectrum by assuming that the Rydberg states of H2 obey Hunds case (d). In this

case the valence electron is treated as being in the Coulomb field of the ionic core

and the analysis follows that for an atomic target, with appropriate factors being

added to account for rovibrational motion of the core [94].

Figure 19 presents a more detailed plot of the spectrum between 361 and

362 nm, together with the prediction of Harries [52]. The correspondence between

STUDIES OF ELECTRON-EXCITED TARGETS 197

FIG. 19. The H2 Rydberg state spectrum between 361 and 362 nm, showing corresponding as-

signments from Ref. [52]. Transitions are to the (n = 8, v = 1) Rydberg states, where v = 0.J +

indicates the nuclear orbital angular momentum of the ionic core and N = L + J + is the total angular

momentum excluding spin. L is the total electronic orbital angular momentum.

experiment and theory is quite good in this region, since the states are well sepa-

rated and perturbations are small. Transitions with N = J +−1 appear to be missing,

most noticeable being the absence of the (1, 0) transition. The relative strengths of

the transitions are predicted reasonably well, and the wavelengths also fit the data.

By assigning transitions in the high Rydberg spectrum, the electron-excited

rovibrational state in the c3u metastable manifold can be studied for the first time.

As an example, preliminary results for the electron-impact excitation functions of

the (v, N ) = (1, 1), (2, 1), and (3, 1) ro-vibrational metastable H2 states are shown

in Fig. 20. These measurements are presently being refined, and these results will

be published in the near future [95].

To complete this section, results from stepwise excitation of metastable targets

selected by the upper detector are described. Since this detector selects a narrow

angular range of deflected targets, the density of targets which enter the detector

is low. Stepwise excitation and subsequent field ionization detection inside this

analyzer therefore require long accumulation times.

The motivation for these experiments is to allow differential cross sections to

be measured as described in Sect. II, with the added benefit that individual states

within the metastable manifold can be studied using the stepwise laser process. Fur-

ther, since the scattering angle of electrons which deflect the selected targets can be

198 Andrew James Murray and Peter Hammond

FIG. 20. Preliminary studies of excitation functions of individual (v, N ) states in the c3 u

*

metastable manifold of states excited by electron impact. The incident electron energy is plotted on the

x axis and the normalized field ionization signal is plotted on the y axis. The excitation functions are

obtained from stepwise laser excitation of these states to the n = 8 Rydberg states.

ascertained from Eq. (4), an energy-selected electron analyzer placed at this angle

will detect the corresponding electrons. By using coincidence techniques between

the energy-selected scattered electrons and the field-ionized laser-excited targets,

cascade contributions can be eliminated without appreciable loss of efficiency.

Experiments using the coincidence technique have yet to be performed, but

the principle has been demonstrated as shown in Fig. 21. In this case, helium

was chosen as the target, since the laser wavelengths for excitation from the 21S0

metastable state to the n1P1 states are well known (Fig. 16). The detection angle

was 6◦ , corresponding to an electron scattering angle θ e = 24◦ for the fast peak

and θ e = 17◦ for the slow peak, with an uncertainty around ±5◦ in each angle. The

301P1 Rydberg state was excited by the laser, since this produces maximum yield in

the field ionization signal. Signal from the manifold of metastable states is shown

for comparison with the field ionization signal where only the 21S0 metastable

state is selected. The time difference between these signals is due to the field

ionization detector being positioned upstream from the metastable detector. The

field ionization signal was measured as a function of time by delaying the laser

pulse to select different portions of the metastable targets passing adjacent to the

detector. Gaussian peaks are fitted to the signal as shown. The field ionization signal

was collected at each data point for 2 × 104 laser pulses, and the maximum number

of ions detected for each laser pulse was around 1 count for 1000 laser pulses. This

compares with the signal in the lower detector, where over 3500 ions would be

detected for an equivalent number of laser pulses. The signal in the upper detector

is significantly reduced due to angle selection of the deflected metastable atoms.

STUDIES OF ELECTRON-EXCITED TARGETS 199

FIG. 21. Field ionization signal and metastable signal in the upper detector. For details, see text.

Signal from the upper detector can be compared to the results of Cubric et al. [46]

for the 21S0 metastable state, assuming that cascades do not play a significant role.

Cubric et al. found the ratio of differential cross sections for θ e = 17◦ compared

to θ e = 24◦ to be 2.94:1. From the results presented in Fig. 21, the stepwise recoil

experiments produce a ratio of 3.11:1, with an uncertainty of ±0.74. This is in

favorable agreement with the more accurate electron-scattering data.

The agreement between these different techniques shows that the stepwise recoil

experiments are a valid method for obtaining differential cross sections. The recoil

results depend on the velocity variation of the target atoms, and are not as accurate

as those obtained using electron scattering. The main advantage of this technique

is that targets can be studied with states too closely spaced to be analyzed using

conventional methods. The resolution of the laser allows cross sections to be

obtained from individual states as in H2, providing new information which cannot

be obtained by other means.

The experiments described here indicate that the recoil technique pioneered by

Bederson and co-workers [8] continues to provide new information about electron-

impact excitation of a wide variety of targets. The technique has been demonstrated

for evaluation of differential cross sections for atoms excited to metastable states,

200 Andrew James Murray and Peter Hammond

and has been shown to provide information about doubly excited states which

decay by fluorescence to metastable states. These latter experiments are currently

being refined, and it is expected that they will provide new information about these

highly excited states.

The principal difference between the experiments described here and the earlier

recoil experiments is the use of laser probing of the excited state. These techniques

allow molecular rotational levels excited by electron impact to be studied for the

first time, and preliminary studies in this area are promising. Electron excitation

functions for these states have been measured for hydrogen, and the first mea-

surements of laser probing of excited recoil targets has been presented. These

results compare well with measurements performed using conventional electron

spectroscopy, and indicate that such measurements are feasible for more complex

targets.

Limitations of the recoil technique have also been shown, and future experi-

ments are being planned to reduce uncertainty due to these restrictions. One of the

main limitations is due to the velocity distribution of the target beam, which pro-

duces a corresponding uncertainty in the calculated electron-scattering direction.

New methods are being developed to reduce this distribution by applying laser

cooling methods. The average velocity and associated distribution can be reduced

using these techniques, with a corresponding increase in sensitivity.

The uncertainty in the electron-scattering direction can also be reduced by

adopting coincidence techniques between the recoil target and the corresponding

electron, since the correlated electron direction is well known from conservation of

momentum and energy. Selection of the momentum of these electrons also removes

cascade contributions, with only a small reduction expected in the counting rate.

The advantages of stepwise laser probing can still be applied in these experiments.

A further limitation of these experiments is due to the resolution of the pulsed

laser, which is severely limited when compared to excitation using a CW laser

source (Fig. 17). Results from laser excitation of H2 (Fig. 18) also show these

limitations, since accurate identification of the transitions to the Rydberg states of

the molecule must be made. Harries [52] has identified some transitions in H2, but

for these experiments to be more generally applicable it is necessary to reconsider

the experimental technique.

These difficulties can be eliminated by adopting a two-step laser process as

shown in Fig. 22. In this case a tunable CW laser excites the metastable target

to an intermediate state, and the pulsed laser further excites the target to a high

Rydberg state from which it is field ionized. This two-step process has a number

of advantages. First, the efficiency of the CW excitation process is high, with up

to 50% of the metastable state population being transferable to the intermediate

state [96]. Second, a stabilized CW ring laser has a linewidth variation of less than

one part in 109. This radiation can therefore not only select individual rotational

and vibrational states in the excited molecular manifold, but can also select targets

STUDIES OF ELECTRON-EXCITED TARGETS 201

FIG. 22. Two-step laser excitation from a metastable target excited by electron impact.

with different isotopic masses [78]. The intermediate states of many molecules are

well known from spectroscopic studies [97], unlike the Rydberg states, which have

not been studied in detail. The results of these spectroscopic studies can therefore

be exploited when determining the electron-excited states under study.

Following CW laser excitation in this scheme, the pulsed laser transfers infor-

mation about the metastable target to the upper Rydberg state, from where it is

field ionized. It is therefore no longer necessary to accurately identify the Ryd-

berg states, since the metastable target state has already been selected. The pulsed

laser and field ionization techniques are exploited to provide an efficient detection

channel with high signal-to-noise ratio as described above.

The disadvantage of this technique is that two lasers are required, with a cor-

responding increase in initial setup and running costs. The experiments are also

more complex, but it has been demonstrated that these difficult experiments are

now possible using current technology. The advantages of using resonant two-

photon excitation from the electron-excited state are expected to be significant,

and it is envisaged that such experiments will be carried out in the near future.

VI. Acknowledgments

We would like to thank the Engineering and Physical Sciences Research Council

in the United Kingdom for funding this work, and would also like to thank our

colleagues at Manchester for providing ideas, advice, and support. In particular,

thanks go to John Reardon, James Harries, and Rob Chandler, who worked as

Ph.D students during the construction and implementation of the apparatus. We

202 Andrew James Murray and Peter Hammond

would also like to thank the mechanical and electronic technicians in the Schuster

Laboratory for providing continuing expertise and support.

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ADVANCES IN ATOMIC, MOLECULAR, AND OPTICAL PHYSICS, VOL. 47

QUANTUM NOISE OF

SMALL LASERS

J. P. WOERDMAN and M. P. VAN EXTER

Huygens Laboratory, Leiden University, 2300 RA Leiden, The Netherlands

N. J. VAN DRUTEN

Department of Applied Physics, Delft University of Technology, Lorentzweg 1

2628 CJ Delft, The Netherlands

I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205

II. Overview of Threshold Behavior. . . . . . . . . . . . . . . . . . . . . . . . . . . . 207

III. Good-Cavity versus Bad-Cavity Regime . . . . . . . . . . . . . . . . . . . . . . . 211

IV. Spontaneous Emission Factor β . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214

V. Cavity QED and β . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219

VI. Magnitude of β . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221

VII. Relaxation Oscillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222

VIII. Disappearance of Fluctuation Threshold . . . . . . . . . . . . . . . . . . . . . . . 227

IX. Petermann Excess Quantum Noise. . . . . . . . . . . . . . . . . . . . . . . . . . . 236

X. Finite Number of Atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242

XI. Concluding Summary. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244

XII. Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246

XIII. References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246

I. Introduction

The theme of this chapter is relevant in view of the present drive toward smaller

lasers. Here one may think of vertical-cavity semiconductor lasers (Chang-

Hasnain, 1998), microdisk and microring semiconductor lasers (Mohideen et al.,

1994; Zhang et al., 1996) photonic bandgap lasers (Lee et al., 1999), rare-

earth microchip lasers (Becher and Boller, 1999), rare-earth microsphere lasers

(Sandoghdar et al., 1996), dye microsphere lasers (Tzeng et al., 1984), micropla-

nar dye lasers (De Martini et al., 1992), one-atom lasers, and one-photon lasers

(An et al., 1994; Löffler et al., 1997; Meyer et al., 1997). Conversely, one may ask

the question how macroscopic laser action emerges out of a one-atom, one-photon

device when the atom and photon numbers are increased.

In this chapter we focus on the question of how the concept “small” should be

quantified; this allows us to compare various lasers in a unified framework. This is

in fact the realm of mesoscopic lasers, i.e., lasers which are between macroscopic

and microscopic. In macroscopic lasers the degrees of freedom of electromagnetic

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ISBN 0-12-003847-1/ISSN 1049-250X/01 $35.00

206 J. P. Woerdman et al.

field and gain medium are effectively continuous variables; in mesoscopic lasers

they are discrete variables, with the one-photon, one-atom laser as ultimate limit.

The discreteness introduces quantum noise, the more so the smaller the number

of degrees of freedom. Since the quantum noise depends on details of the system,

the universality of the macroscopic laser gets more and more lost the deeper one

penetrates into the mesoscopic domain (Rice and Carmichael, 1994). Starting

from an ideal, amplitude-stabilized coherent oscillator, the route branches into a

manifold of parallel paths to a variety of nonlinear amplifiers of quantum noise.

These generally still allow a semiclassical description. Much further along the way,

a true quantum description becomes gradually essential (Brecha et al., 1995), in

particular at the end of the route where we reach the cavity quantum electrodynamic

(QED) limit in the form of a one-atom, one-photon device. The latter may come in

many varieties (Löffler et al., 1997; An et al., 1994; Kimble, 1994); a spectacular

example is a deterministic device that emits a single photon upon command (Kim

et al., 1999). The transition between the semiclassical limit and the quantum limit

is of course very vague; this is the realm of mesoscopic physics.

There is a close analogy with the mesoscopic aspects of a material phase tran-

sition. The laser threshold transition of a macroscopic laser can be seen as a

thermodynamic phase transition in a classical macroscopic system (Sargent et al.,

1974). When the system involved is made smaller, the universal nature of any

phase transition is affected by finite-size effects: e.g., the melting temperature of

a cluster of, say, 60 H2O molecules differs from the liquid-phase melting temper-

ature (Berry, 1994). This difference is nonuniversal: when considering molecules

other than H2O, the percentage “correction” of the melting temperature will de-

pend on the specific molecule involved. For sufficiently small clusters, a quantum

description becomes essential, certainly so at the end of the route, where we deal

with a single molecule. Note, however, that a cluster such as C60 is still an almost

classical body because of its many internal degrees of freedom and their possible

couplings to the environment (Arndt et al., 1999).

Some popular notions that hold true for a macroscopic laser are as follows

(Wiseman, 1997):

1. The threshold condition occurs when the round-trip gain equals the round-

trip loss.

2. The laser linewidth does depend on the cavity linewidth but not on the gain

linewidth.

3. The photon statistics of a laser change when the laser goes through threshold.

In fact, as we will see, these statements generally break down for small lasers, long

before we hit the one-photon, one-atom limit.

A lot of what we have said above is not really new, in the sense that much of

it can be found in the semiclassical laser theories developed around 1970 (Haken,

1966; Lax, 1966; McCumber, 1966; Risken, 1970; Seybold and Risken, 1973;

Sargent et al., 1974). In those days, however, theory was far ahead of experiment,

QUANTUM NOISE OF SMALL LASERS 207

so it was mainly the generic theoretical results that made a lasting impression;

the “special” cases that, in our present language, correspond to routes into the

mesoscopic domain were often forgotten (in fact, some of the theory papers that

stimulated us were hardly ever cited). It did not help either that sometimes such a

“special” case was labeled as experimentally unrealistic (that is, around 1970).

A direct comparison of laser theories (old or new) is impossible once we are in

the mesoscopic domain, since the theories start from different models and thus lead

in principle to different results; generic results are found only in the macroscopic

limit. Since these models are approximations of physical reality regarding level

scheme, pumping mechanism, hierarchical ordering of relaxation rates, etc., it is

only by comparison with experiments that we can decide whether a certain model

description is realistic for a certain laser. Moreover, for a given laser model, theories

may be developed with various levels of sophistication. All this explains why there

are so many laser theories.

It is not our ambition to give a systematic overview of this confusing situation.

Instead, we will ad hoc draw on existing theories (including our own), compare

them with experiments, and point to cases where understanding is lacking. We will

emphasize throughout a mesoscopic perspective.

We start with a very simple laser model, namely, a single-mode laser based on a

homogeneously broadened gain transition. We assume an ideal four-level scheme,

i.e., negligible population in the lower laser level (see Fig. 1). For such a laser the

rate equations for the number of intracavity photons s and the number of inverted

atoms N are

Ṅ = S − βγ s N − γ N , (2)

FIG. 1. Level scheme of a laser. The upper level is pumped at a rate S, the upper level decays at a

rate γa , and the lower level decays at a rate γb . We assume γb ≫ γa so that the inversion decay rate

γ equals γa . A fraction β of the spontaneous emission is in the laser mode which is populated by

s photons. The laser cavity has an intensity outcoupling rate Ŵc and a field outcoupling rate κ, with

Ŵc = 2κ. The dipole dephasing rate of the lasing transition a → b is denoted as γ⊥ .

208 J. P. Woerdman et al.

where S is the pump rate, κ is the cold-cavity damping rate of the field, and γ is

the inversion damping, which equals, for an ideal four-level laser, the upper-level

decay rate. Note that 2κ is the damping rate of the intracavity intensity or photon

number; later in the chapter we will often refer to 2κ as Ŵc , as in van Exter et al.

(1995). Note also that in writing Eqs. (1) and (2) we have assumed an (effectively)

frequency-independent gain, i.e., the polarization of the gain medium (which has

a damping rate γ⊥ ) has been adiabatically eliminated. This is allowed as long

as γ⊥ ≫ κ. The cross-terms Ns and sN in Eqs. (1) and (2) account for the gain

saturation; this nonlinearity is essential for the laser dynamics. The parameter β in

Eqs. (1) and (2) is of a phenomenological nature: it is the fraction of spontaneous

emission of an inverted atom that is emitted in the laser mode (a fraction 1 − β

“escapes”). In writing Eqs. (1) and (2) it has been assumed that β ≪ 1; i.e., we stay

within a semiclassical description where spontaneous emission noise is accounted

for in a perturbative sense. Setting the time derivatives in Eqs. (1) and (2) equal to

zero, we find for the steady-state photon number s0 = s
(see also Siegman, 1986)

1

s0 = [(M − 1) + (M − 1)2 + 4M β], (3)

2β

where M ≡ S/Sthr is the dimensionless pump parameter and Sthr ≡ 2κ/β is the

threshold pump rate.

We have plotted Eq. (3) in Fig. 2 for the case β = 10−8 . Far above threshold

(M ≫ 1), we find

s0 = (M − 1)β −1 , (4)

FIG. 2. Steady-state photon number, s0 , as a function of the pumping parameter M ≡ S/Sthr , for a

laser with β = 10−8 . Regime III corresponds to linearized semiclassical theory, regime II to nonlin-

earized semiclassical theory, and regime I to quantum theory.

QUANTUM NOISE OF SMALL LASERS 209

FIG. 3. Steady-state photon number s0 versus S/ Ŵc , where S is the pumping rate and Ŵc the cavity

intensity decay rate for a laser with β = 10−8 , 10−6 , 10−4 , 10−2 , and 1.

precisely at threshold (M = 1)

s0 = β −1/2 , (5)

1

s0 = . (6)

1−M

The “sharpness” of the threshold transition, defined as the width of d ln(s)/d lnM,

is ∼β −1/2 , when expressed in the dimensionless parameter M. For β → 1 the

jump is more and more smoothened due to spontaneous emission noise; for β = 1

it disappears completely, leading to a thresholdless laser (Fig. 3). Thus β is a

parameter that characterizes the “system size”; the concept of the laser threshold is

well defined only in the “thermodynamic” limit β −1 → ∞ (Rice and Carmichael,

1994).

For the steady-state inversion number N0 we find

N0 M s0

= = , (7)

Nthr 1 + βs0 s0 + 1

where Nthr = 2κ/βγ is the inversion number at threshold. This implies that the

equilibrium round-trip gain is smaller than the round-trip loss, the more so the

smaller the photon number s0 is, i.e., generally the more so the smaller the laser

is. The gain deficit is made up for by the spontaneous emission input in the mode.

In the limit β → 1 the concept of round-trip gain has lost its significance, since

210 J. P. Woerdman et al.

stimulated and spontaneous emission are no longer meaningful concepts when the

active medium can interact with only one mode of the electromagnetic field.

The merit of introducing the phenomenological parameter β is that it leads to

an expression for s0 as simple as Eq. (3). This expression has generic validity,

i.e., it survives in other models (An and Feld, 1997; Sommers, 1982; Koganov

and Shuker, 1998; Protsenko et al., 1999). If the variables of the gain medium can

be adiabatically eliminated (i.e., κ ≪ γ , γ⊥ ), we are left with the laser field as

the only independent variable which “slaves” the gain variables. In this case of a

so-called class-A laser, β is the only threshold parameter. Equation (3) represents

then a universal route through the mesoscopic domain, from the macroscopic to

the microscopic limit, as far as the steady-state photon number is concerned.

After the above discussion of the steady-state behavior we give now an impres-

sion of the multitude of theories of laser fluctuations. For this case we add noise

sources to Eqs. (1) and (2) and allow ṡ = 0 and Ṅ = 0. Semiclassical laser theories

assume s0 ≫ 1. Quantum corrections thereupon (due to the operator nature of the

field) are of the order of the inversion photon number at threshold, sthr ∼ β −1/2

(Risken, 1970; Seybold and Risken, 1974). As long as sthr ≥ 10 (i.e., β ≤ 10−2 ),

semiclassical theory is basically sufficient. Even for β as large as 0.1, the quan-

tum corrections, despite being large, are not yet dominant. (Coincidentally, these

numbers are not so different from mesoscopic cluster physics, as discussed in

Sect. I).

The labels I, II, and III in Fig. 2 are useful to mark the validity of various class-A

laser theories (Fig. 2 does this for β = 10−8 ). Restricting ourselves first to the

semiclassical approximation, we find that far above threshold (M − 1 ≫ β −1/2 )

the inversion is pinned, leading to a strong reduction of the amplitude fluctuations.

The fluctuations can then be linearized around the steady state, which greatly

simplifies the situation. Such theories (Sargent et al., 1974; Haken, 1966; Kolobov

et al., 1993) are valid in regime III. Close to threshold (regime II) the linearization

breaks down and the full semiclassical equations have to be used (Risken, 1970;

Seybold and Risken, 1974; Gnutzmann, 1998).

Far below threshold the photon number becomes sufficiently small that a semi-

classical description is inadequate. This applies to regime I; a full quantum de-

scription is then required (Löffler et al., 1997). When we increase the value of β,

as in Fig. 3, the (dashed) border lines between the regimes I, II, and III in Fig. 2

shift upward until for β = 1 a quantum theory is required over the full pumping

range; the essentially classical concepts of threshold, amplitude stabilization, and

inversion pinning have then disappeared (Rice and Carmichael, 1994).

If we do not deal with a class-A laser, i.e., if the inversion and /or polarization

of the gain medium cannot be adiabatically eliminated, Eq. (3) remains valid but

the fluctuation properties near threshold will, at least in principle, also depend

on other parameters. A number of examples of this will appear in the rest of the

chapter.

QUANTUM NOISE OF SMALL LASERS 211

As we saw in Sect. II, in a conventional laser the optical field is a slow variable that

slaves the inversion and the polarization of the gain medium, κ ≪ γ , γ⊥ (class-A

laser). In practice, microlasers rarely belong to class A, and theories that make

the class-A assumption therefore have limited usefulness (Pedrotti et al., 1999;

Protsenko et al., 1999). The reason is that, when moving to microlasers, the decay

rate of the intracavity intensity,

c

Ŵc = 2κ = − ln(R1 R2 ), (8)

2L

usually not compensated by an increase of the mirror reflectivity product R1 R2 .

The violation of the class-A condition can take several forms. One example is the

class-B laser, κ ≫ γ , which is discussed in detail in Sects. VII and VIII. Another

example is the so-called bad-cavity laser, κ > γ⊥ , as opposed to the good-cavity

laser (κ < γ⊥ ) which is implied by class A. Note that an ideal four-level laser

scheme implies γb ≫ κ (see Fig. 1) and thus leads automatically to the good-

cavity condition, since γ⊥ = γ + γb + 2γcoll ≫ κ. In this section we compare the

good-cavity and the bad-cavity regimes.

In the bad-cavity regime the gain linewidth is narrower than the cavity linewidth;

this has dispersive consequences which can be expressed via the group refractive

index n gr . Using the Kramers–Kronig relations, we find (van Exter et al., 1995)

dn κ

n gr ≡ n + ω = n 0gr + , (9)

dω γ⊥

where n 0gr is the group refractive index of the unpumped gain medium (n 0gr = 1

for a gas laser) and where the term κ/γ⊥ represents the anomalous dispersion

associated with the pumped, resonant gain medium. The effective optical length

n gr L of a bad-cavity laser can thus be much larger than the optical length of the

unpumped cavity (n 0gr L) if n gr ≫ n 0gr ; this shows up in the phenomenon of mode

pulling (Casperson and Yariv, 1973).

Operation in the bad-cavity instead of the good-cavity regime has a dramatic

effect on the linewidth of the laser. The quantum-limited linewidth due to diffusion

of the phase of the laser light is given by the generalized Schawlow–Townes

expression (Haken, 1966; Lax, 1966; Kolobov et al., 1993; Kuppens et al., 1994;

van Exter et al., 1995; Wiseman, 1999),

1 κγ⊥ β κγ⊥

ωℓ = = , (10)

s0 γ ⊥ + κ (M − 1) γ⊥ + κ

212 J. P. Woerdman et al.

In the good-cavity limit κ ≪ γ⊥ , which is almost always (implicitly) assumed, this

reduces to the “standard” Schawlow–Townes expression found in many textbooks

(Siegman, 1986; Sargent et al., 1974),

κ

ωℓ = . (11)

s0

When expressed in the intensity decay rate Ŵc instead of the field decay rate κ,

Eq. (11) reads ωℓ = Ŵc /2s0 . In the bad-cavity limit the result is

γ⊥

ωℓ = . (12)

s0

Equation (12) is in fact the famous formula in the form originally given by

Schawlow and Townes (1958). Equations (11) and (12) are also valid below thresh-

old if multiplied at the right-hand side by a factor of 2, which accounts for the

amplitude fluctuations which are not suppressed since below threshold there is no

gain saturation that can stabilize the intensity. When proceeding through threshold

from below, the linewidth decreases abruptly due to the sudden increase of s0 by

a factor of order β −1 . For a “β = 1” laser the threshold has disappeared and the

linewidth decreases continuously as a function of the pump strength (Yamamoto

and Imamoglu, 2000).

Figure 4 shows an experimental example of the good-cavity limit of the

Schawlow–Townes linewidth for a semiconductor laser. Such a laser has typically

FIG. 4. Inverse linewidth of a Hitachi HLP1400 AlGaAs semiconductor laser plotted as a function

of the total output power from both facets. (From van Exter et al., 1992, copyright 1992 IEEE.)

QUANTUM NOISE OF SMALL LASERS 213

γ⊥ ≈ 1013 s −1 and κ ≈ 1011 s −1 (van Exter et al., 1992). The measured linewidth

is inversely proportional to the output power Pout = 2κhνs0 . For completeness we

note that the fit in Fig. 4 was not based on Eq. (11) but on

κ

ωℓ = n sp (1 + α 2 ). (13)

s0

Here n sp ≡ Na /(Na − Nb ) is the incomplete inversion factor that accounts for the

fact that we do not deal with an ideal four-level laser (see Fig. 1) and α is the

linewidth enhancement parameter that accounts for detuning of the cavity mode

and the gain profile. (For simplicity we neglect these complications in the rest of

the chapter.)

Figure 5 shows an experimental example of the bad-cavity limit of the

Schawlow–Townes linewidth for a short HeNe 3.39-μm laser (Kuppens et al.,

1994); the plot shows data for the product νℓ Pout versus Ŵc2 and the solid and

dash-dotted fit curves represent Eq. (10), with and without including the n sp factor

as in Eq. (13), using s0 = Pout / Ŵc hν, Ŵc = 2κ, and n sp = 1.3. Using the standard

Schawlow–Townes formula from the textbooks (i.e., implicitly assuming good-

cavity conditions) leads to the dashed line in Fig. 5 as a fit curve, i.e., a completely

meaningless fit.

FIG. 5. Linewidth–power product of a HeNe 3.39-μm laser at zero detuning as a function of Ŵc2 ,

where Ŵc is the cavity decay rate. The points are measured data, corresponding with different combi-

nations of mirrors with reflectivities R = 8%, 30%, 70%, 90%, and 98%. The dashed line is based

on Eq. (11), whereas the solid and dash-dotted curves are based on Eq. (10) multiplied by n sp , with

n sp ≡ 1 and n sp = 1.3, respectively. (From Kuppens et al., 1994, copyright 1994 APS.)

214 J. P. Woerdman et al.

Interestingly, one can derive the general result Eq. (10) from the good-cavity

result Eq. (11), namely, by appreciating that the optical length of the cavity, and

thus the photon cavity lifetime, are proportional to n gr as given by Eq. (9). We

should therefore introduce a “dressed” cavity loss rate κ/n gr in Eq. (11) instead of

the “bare” cavity loss rate κ. This immediately leads to Eq. (10).

A side issue when pursuing the bad-cavity limit is how far R1 R2 in Eq. (8) can

be reduced before the laser stops being a laser and turns into a source of amplified

spontaneous emission only. By requiring that the reflective feedback fraction of

the intracavity intensity by the mirrors be larger than the fraction of spontaneous

emission into the laser mode and assuming saturation of the inversion, we find as

condition

R1 R2 > β 2 . (14)

Thus β appears again in this context. Equation (14) should not be confused with

the threshold condition; in fact, Eq. (14) distinguishes between feedbackless

amplified spontaneous emission and a subthreshold laser.

As we have seen, the threshold behavior of a class-A laser, in which the gain

medium is slaved to the field, is governed by the spontaneous emission factor β. A

calculation of β deals basically with mode counting, i.e., with the cavity geometry.

An accurate calculation is often lengthy and tedious. It involves a summation or in-

tegration of the atom–field coupling over all optical modes of a three-dimensional

cavity and thereby touches the heart of quantum electrodynamics. However, as out-

lined by van Exter et al. (1996), the theory can be greatly simplified by introducing

a few assumptions.

Figure 6 sketches a typical system for which we will calculate β. The emitters

in the active medium are for convenience denoted by “atoms” with transition

dipoles μ12 , although they might equally well be molecules, electrons, excitons,

or any other entities interacting with light. The atoms radiate spontaneously in a

multitude of directions and frequencies. It is now our task to determine the fraction

β of photons emitted into a single discrete mode, which occupies inside the cavity

an optical volume Vcav and subtends a space angle cav . This mode has a finite

spectral width due to outcoupling at the mirrors. The remaining optical modes are

treated as a continuum.

The calculation simplifies considerably when a quasi-one-dimensional

approach is taken, in which the optical continuum is subdivided into modes that

interact with the discrete cavity mode, through the mirrors, and modes that do not.

The former part of the continuum is associated with the “longitudinal” modes, as

they have their wave vectors oriented more or less along the cavity axis, whereas

QUANTUM NOISE OF SMALL LASERS 215

FIG. 6. Typical geometry for which β is calculated. (From van Exter et al., 1996, copyright 1996

APS.)

the latter part may then be associated with the “transverse” modes. This separa-

tion is depicted in Fig. 7. The various arrows show the pump as energy supplier,

additional loss of atomic coherence due to collisional dephasing (rate γcoll ), spon-

taneous emission to the transverse-optical continuum, coherent coupling to the

discrete cavity mode with a coupling constant g ≡ μ12 E 0 /h, where E 0 is the vac-

uum field, and optical loss out of this mode (loss rate κ). We restrict our attention

to the weak-coupling regime, i.e., g ≪ κ (see also Sect. V). In that case the co-

herent coupling and cavity loss combine to an effective exponential decay from

the excited atomic state to the longitudinal-optical continuum outside the cavity

(Jin et al., 1994; Sachdev, 1984). The spontaneous emission factor β is then

equal to the relative contribution of the latter decay to the total spontaneous emis-

sion rate γ , which also includes (and for β ≪ 1 is dominated by) decay to the

FIG. 7. Schematic diagram of the couplings between the atomic excitation, the discrete cavity mode,

and the optical continuum. (Adapted from van Exter et al., 1996, copyright 1996 APS.)

216 J. P. Woerdman et al.

FIG. 8. Spectra of the spontaneous emission and the cavity resonance. (Adapted from van Exter

et al., 1996, copyright 1996 APS.)

transverse-optical continuum. For the atomic system the radiative decay (as T1 pro-

cess) and collision dephasing (as pure T2 process) combine to γ⊥ = γ + 2γcoll .

In the literature one finds basically two different approaches to calculate β.

Although this is often not clearly stated, these approaches are valid in two mu-

tually excluding regimes, namely, the good-cavity (κ ≪ γ⊥ ) and the bad-cavity

(κ ≫ γ⊥ ) regime. The cavity linewidth κ and the atomic linewidth γ⊥ are indi-

cated in Fig. 8.

In the good-cavity regime the cavity mode has a relatively well-defined fre-

quency. The standard approach is then to assume lateral confinement, by setting

the optical quantization volume Vquant equal to the volume Vcav taken up by the

cavity mode, and simply counting the number of modes p with eigenfrequencies

falling underneath the atomic spectral profile. At resonance this “mode count”

gives (Yamamoto et al., 1991, Baba et al., 1991)

1 1 λ3 ω

β= = 2

× × , (15)

p 4π Vcav γ⊥

where λ and ω are the optical wavelength and optical frequency. Equation (15)

shows that β is basically the inverse of the modal volume, in units of λ3 , multiplied

by the Q factor of the atomic transition. Therefore, it is not only the cavity volume

Vcav that determines how “mesoscopic” a laser is; the atomic linewidth γ⊥ is as

important. The product of Vcav and γ⊥ determines how many free-space modes are

on “speaking terms” with the active medium.

QUANTUM NOISE OF SMALL LASERS 217

(see Gutiérrez and Yáñez, 1997). The problem of counting normal modes in a

cavity was apparently introduced by Lorentz during a guest lecture in Göttingen,

addressing black-body radiation. He posed to the mathematicians in the audience

the problem of proving that the mode count is independent of the shape of the

cavity and thus depends only on the volume (if the latter is large enough). Hilbert,

who was in the audience, predicted that this conjecture would not be solved during

his lifetime. Surprisingly, Weyl, a former student of Hilbert, only 2 years later was

able to prove the conjecture.

In the bad-cavity regime (κ ≫ γ⊥ ) the cavity modes are spectrally broad and

it is common to consider the problem from the atomic point of view. When the

emitted light is followed on its path between the mirrors, interference is found to

lead to radiation enhancement for some emission angles and suppression for others

(Yamamoto et al., 1992; Björk et al., 1991, 1993). As κ ≫ γ⊥ this modification

will be more or less constant over the full spontaneous emission spectrum, and for

a very thin (≪ λ) active medium positioned in an antinode of the optical field one

finds at resonance (Matinaga et al., 1993; Yamamoto et al., 1992)

cav 4

β= , (16)

8π 1− R

where cav is the solid angle subtended by the cavity mode and R is the intensity

reflectivity of the cavity mirrors. For a much thicker active medium, which extends

over many nodes and antinodes, the “position-averaged” β is a factor of 2 smaller

than the value given by Eq. (16).

Although this is not at all obvious, Eqs. (15) and (16) are limiting cases of

a single, more general form. This form can be derived by making the following

assumptions:

1. The radiating dipoles μ are randomly oriented in space.

2. The active medium is spread out over many nodes and antinodes in a volume

not exceeding the optical mode volume Vcav .

3. The total spontaneous emission rate is equal to its value in free space.

We first discuss these assumptions in some detail, before giving the resulting

expression for β. Assumption 1 implies that the vector nature drops out of the

problem, and assumption 2 implies that the active dipoles interact on average with

the same electric-field strength. Together they allow us to eliminate the atomic

transition dipole, μ (see Fig. 6), thus clearly showing the geometric nature of the

problem. If desired, some of the restrictions can be easily removed. For instance,

β can be increased by preferential alignment of the dipoles μ along the field

polarization; this increase is at most a factor 3. Preferential positioning of the

dipoles in the antinodes of the field yields another factor 2.

218 J. P. Woerdman et al.

less equal to its free space value, is a crude assumption, as we know that the cavity

leads to enhanced spontaneous emission in some modes and we are in fact trying

to calculate this enhancement and its effect on β. However, the spontaneous emis-

sion will generally be enhanced only for relatively few modes, whereas it remains

unaffected or will even be suppressed for other modes. Therefore, the cavity leads

mainly to a directionality, i.e., a redistribution over phase space of the emitted pho-

tons, but its effect on the total emission rate γ is generally small and assumption 3

is approximately valid for cavities with relatively small β values (e.g., β < 0.1).

Experimentally, it has been found very difficult to realize β > 0.1; see Sect. VI.

These assumptions allow a calculation of β based on a dipolar atom–field

interaction Hamiltonian combined with Fermi’s “golden rule” for decay into a

continuum of final states. We introduce β(ω) for monochromatic emitters,

1 λ3 + ω , (κ/2)2

β(ω) = (17)

4π 2 Vcav κ (ω − ωcav )2 + (κ/2)2

and integrate β(ω) over the free-space emission spectrum L(ω),

β = dω β (ω)L(ω), (18)

with

γ⊥ /(2π )

L(ω) = . (19)

(ω − ωatom )2 + (γ⊥ /2)2

At resonance (ωcav = ωatom ), the final result becomes

1 λ3 ω

β= , (20)

4π 2 Vcav κ + γ⊥

Substituting now Vcav = AL, in Eq. (20), where A is the mode cross-sectional area

and L is the cavity length, and introducing the diffraction result for the solid angle

of the cavity modes,

2λ2

cav ≈ , (21)

A

we find for the resonant case ωcav = ωatom ,

cav 2ω f sr /π cav 2 κ

β= = . (22)

8π κ + γ⊥ 8π 1− R κ + γ⊥

QUANTUM NOISE OF SMALL LASERS 219

Here ωf sr is the free spectral range of the longitudinal cavity modes; note that

1− R ωf sr

κ= ωf sr = , (23)

π F

where F is the cavity finesse. Equation (22) generalizes Eq. (16), and reduces to

it in the bad-cavity regime, κ ≫ γ⊥ , apart from a factor of 2. This factor arises

since we have assumed the atoms to be evenly distributed over the cavity volume,

i.e., over nodes and antinodes, instead of being concentrated in the antinodes as

assumed for Eq. (16).

Whether Eq. (20) or Eq. (22) is more convenient depends in practice on the

geometry of the cavity. Anyway, it is now obvious that to obtain a large β, both the

cavity decay rate κ and the atomic decay rate γ⊥ have to be small.

The generalization of Eq. (15) into Eq. (20) can also be seen differently, namely,

by introducing the group refractive index n gr in the mode-counting recipe leading to

Eq. (15). The density of modes in a space filled with the gain medium is (Verdeyen,

1989)

ω2

ρ(ω) = n 2 n gr . (24)

π 2 c3

This leads to an extra factor n gr in Eq. (15); when using Eq. (9) we obtain again

Eq. (20) (Kuppens et al., 1994; van Exter et al., 1995). Note that off-resonance

tuning, i.e., ωcav = ωatom , will lead to different results.

Instead of “dumping” the bad-cavity aspects into an effective β, as was done

in Eqs. (20) and (22), one may also stick with the geometrically defined β as in

Eq. (15). In that case the threshold behavior of the laser can be said to depend

on two parameters, namely, the geometric β and the ratio γ⊥ /κ, instead of one

parameter, i.e., the effective β.

As mentioned in Sect. II, rate equation theories of the laser have been developed

on several levels of sophistication. The (phenomenological) spontaneous emission

factor β can be recognized in such theories as a relatively simple algebraic function

of the evolution rates of field and gain medium. The rates that may potentially ap-

pear in β are κ, γ , γ⊥ , and g (Kimble, 1994). The various mesoscopic routes from

a macroscopic laser to a one-photon, one-atom microscopic device correspond in

cavity QED parlance to different hierarchical orderings of these rates.

In the simplest possible macroscopic case, namely, a single-mode, homoge-

neously broadened, four-level class-A laser as considered in Sect. IV, one finds

220 J. P. Woerdman et al.

2g 2

β= (25)

γ (γ⊥ + κ)

which is valid as long as β ≪ 1. Although Eq. (25) looks very different from

Eq. (20) or Eq. (22), it is in fact identical; this follows by substitution of g =

μ12 E 0 /h in Eq. (25), using E 0 = (hω/ǫ0 Vcav )1/2 for the vacuum field and γ =

ω3 μ212 /π ǫ0 hc3 for the spontaneous emission rate into free space. In cavity QED the

parameter (β)−1 is known as the “critical” photon number scrit (Kimble, 1994); in

that context the phenomenological interpretation of β as the fraction of spontaneous

emission in the laser mode is irrelevant.

Equations (20), (22), and (25) remain valid as long as they predict values β ≪ 1.

However, they lose their validity, at least if we want to interpret β as the fraction

of spontaneous emission in the laser mode, when the radiative properties of the

active atoms are seriously affected by the electromagnetic boundary conditions

represented by the cavity. Incorporation of this aspect implies tedious calculations

for each specific cavity configuration. Instead, we will keep using the free-space ex-

pression γ as the spontaneous emission rate of an atom in the cavity, but normalize

the resulting value of β “by hand,” by introducing

β

β∗ = (26)

1+β

as the spontaneous emission factor of a cavity QED laser (van Exter et al., 1996; Jin

et al., 1994; An and Feld, 1997). Henceforth we will drop the asterisk as superscript

and refer to a “β = 1” laser. The ad hoc procedure contained in Eq. (26) does of

course no justice to the full richness of a cavity QED laser, but it catches the

semiclassical aspects of such a laser. It is, for instance, a valid description of a

one-atom laser with random atomic injection and small Rabi rotation; a one-atom

laser shows nonclassical photon statistics only if the atoms are injected regularly

or if the Rabi rotation during an atomic transit is at least of the order of 1 rad

(An and Feld, 1997).

It is interesting to see how the magnitude of β compares with the usual cate-

gorization of the weak- and strong-coupling regimes of cavity QED. In the weak-

coupling limit,

g ≪ κ, γ , γ⊥ , (27)

QUANTUM NOISE OF SMALL LASERS 221

g ≫ κ, γ , γ⊥ (28)

and leads to oscillatory Rabi exchange of excitation between field and gain medium;

the field acquires then a strongly nonclassical signature (Löffler et al., 1997; Meyer

et al., 1997; Kimble, 1994). Using Eqs. (25) and (26) and imposing as condition

β ∗ = 1, we find that a “β = 1” laser requires

This may be called the strong-field limit (Brecha et al., 1995); it says that a sin-

gle photon is able to saturate the inversion. This must not be confused with the

strong-coupling limit Eq. (28); the latter is not necessary to realize a “β = 1” laser

(Yokoyama and Brorson, 1989). On the other hand, we cannot afford to stay in the

weak-coupling limit Eq. (27) if we want to realize a “β = 1” laser; g must be larger

than at least one of the trio γ , γ⊥ , κ. A theoretical study of the case g ≥ κ has

been reported, under the heading “mesomaser” (Balconi et al., 1995); in Sect. VIII

we will encounter the case g ≥ γ . Other connections between cavity QED theory

and mesoscopic lasers will be pointed out in Sect. X.

VI. Magnitude of β

Which β values can be realized in practice? We start with some conventional lasers.

For a typical gas laser such as the HeNe 633-nm laser, one has β ≈ 10−8 (Siegman,

1986). A small, high-gain HeXe gas laser at 3.51 μm can have β = 10−5 –10−6

(van Eijkelenborg et al., 1998). Index-guided edge-emitting semiconductor lasers

have β ≈ 10−5 ; in case of gain guiding one has β ≈ 10−4 (Petermann, 1979;

Arnold et al., 1983; Streifer et al., 1982). Semiconductor vertical-cavity surface

emitting lasers have β = 10−3 –10−4 (Shin et al., 1997). All these β values have

been deduced from the sharpness of the threshold transition and have been found

to be consistent with Eqs. (20) and (22).

Special microring and microdisk semiconductor microlasers have been reported

to have β values in excess of 0.1 (Mohideen et al., 1994; Zhang et al., 1996). How-

ever, these values have not been corroborated by study of the fluctuation prop-

erties but are based on steady-state output versus pump characteristics only; this

method becomes rather unreliable when β approaches unity. In an atomic system a

“β ≈ 1” laser has already been realized, be it effectively in the semiclassical limit

(An et al., 1994; An and Feld, 1997). In a nonlaser context β-values very close to

unity have been realized at microwave frequencies in cavity QED experiments in

the strong-coupling regime, i.e., corresponding to strongly nonclassical features

222 J. P. Woerdman et al.

(Rempe et al., 1990). More recently, this work has been extended into the optical

domain (Hood et al., 1998; Münstermann et al., 1999).

Semiconductor lasers are very many orders of magnitude smaller than gas lasers

and yet their β values are only a few orders of magnitude larger than for gas lasers.

This is of course a consequence of the fact that not only the cavity volume but

also the spectral width of the gain transition enters into Eq. (20); the ratio of these

spectral widths is typically 2 × 1013 Hz/2 × 109 Hz ≈ 104.

Continuing this line of thought, we have tried to obtain higher β values by

using a solid-state “atomic” gain medium, such as Nd3+ :YAG or Nd3+ YVO4.

These systems offer a much larger gain coefficient than a gas laser, i.e., they

can be made much smaller; furthermore, their (homogeneous) linewidth is still

modest (γ⊥ /π ≈ 220 GHz at 300 K). When substituting material parameters as

given in the Casix crystal guide (1997/1998) into Eq. (20) for these systems,

one finds that β ≈ 0.1 requires Vcav ≈ 100 μm3. It seems feasible to realize

such a laser since the gain coefficient of fully inverted Nd3+ :YVO4 is ∼2%/μm

(at 300 K), so a cavity length of 10 μm and a mirror reflectivity product

R1 R2 ≥ 80% would be sufficient. This implies a mode diameter of ∼3 μm. In

this numerical example we have κ ≈ 250 × 109 s−1 and γ⊥ ≈ 780 × 109 s−1 in

Eq. (20), i.e., we are between the good-cavity and bad-cavity regimes. Further

decreasing γ⊥ (e.g., by cooling) does not substantially increase β, unless we si-

multaneously decrease κ. The only published work along these lines (Sandoghdar

et al., 1996) used a Nd3+ -doped-glass microsphere; a value of β ≈ 4 × 10−2 was

deduced by using a mode-counting formula like Eq. (15).

The relaxation oscillation of a laser is an oscillatory exchange of excitation between

the optical intensity and the inversion. Relaxation oscillations are well developed

when the inversion damping is much smaller than the cavity photon damping, i.e.,

γ ≪ κ, also called a class-B laser. Practical microlasers tend to be in this class,

since their small length leads to a large value of κ (in practical microlasers the

small length is at most partly compensated by an increase in mirror reflectivities).

Furthermore, the spontaneous emission noise source that excites the relaxation

oscillation becomes increasingly stronger when the laser becomes smaller (more

precisely, when β increases). Therefore, microlaser theories that neglect the relax-

ation oscillation (Jin et al., 1994; Protsenko et al., 1999; Yamamoto and Imamoglu,

1999) are of limited use.

Naively, one might think that for the case γ ≪ κ the field can be adiabatically

eliminated, leaving only the inversion as independent degree of freedom. This

would then be in the same spirit as the reduction to the field as the only independent

degree of freedom for the case γ ≫ κ. However, this is not correct, as can already

be guessed from the fact that the evolution equations for photon number and

QUANTUM NOISE OF SMALL LASERS 223

inversion number are not symmetric [cf. Eq. (1) and Eq. (2)]. The key point is

that the adiabatic elimination of the field in a class-B laser (γ ≪ κ) leads not to

a stable solution but to a limit cycle solution, i.e., the relaxation oscillation.

The relaxation oscillation is a semiclassical concept, i.e., it refers to a laser

with many photons and many atoms. The theoretical description starts from the

Maxwell–Bloch equations; we adiabatically eliminate the polarization, i.e., we

assume the good-cavity regime, and rewrite the equations in terms of the optical

intensity (instead of the optical field). This leads to the set of rate equations already

given as Eqs. (1)–(2). By linearizing around the steady state one finds (McCumber,

1966; Lax, 1966)

d s −Ŵs γ βs0 s fs

= + , (30)

dt N −Ŵc −ŴN N fN

Langevin noise sources f s and f N . The assumption N ≪ N0 is an excellent

approximation since for a class-B laser the damping time of the inversion is much

larger than that of the cold cavity, (Mγ )−1 ≫ κ −1 , so that the effect of the (poten-

tially wild) intensity fluctuations on the inversion is almost completely averaged

out. Note, however, that it is incorrect to set N ≡ 0, since this will “kill” the

relaxation oscillation (Protsenko et al., 1999). The assumption s ≪ s0 will be

relaxed in Sect. VIII. Following Lax (1966), we have introduced in Eq. (30) damp-

ing rates of the fluctuations, namely, a “photonic” damping Ŵs and an “atomic”

damping ŴN , defined as

Ŵc βŴc

Ŵs = ≈ , (31)

s0 + 1 M −1

ŴN = γ {1 + β(s0 + 1)} ≈ Mγ , (32)

where we assume s0 ≫ 1. Note that Ŵs is the net damping rate of the intensity

fluctuations in the “hot” cavity, i.e., including the gain medium. We emphasize

that the fluctuations in the photon number and the inversion are both intrinsically

damped, so that the steady state of a class-B laser is indeed a stable solution. Note

also that photonic damping plays no role for a class-A laser, since the condition

γ > κ = 21 Ŵc implies in almost any practical situation that Ŵs ≪ ŴN [see Eqs. (31)

and (32)]. Very close to threshold, however, photonic damping does play a role in

a class-A laser (see Oraevsky, 1990).

The linearized matrix equation (30) can be converted into a second-order dif-

ferential equation with a deterministic part,

d 2 s ds 2

2

+ (ŴN + Ŵs ) + ωr o + ŴN Ŵs s = 0, (33)

dt dt

224 J. P. Woerdman et al.

where

γr o = 21 (ŴN + Ŵs ), (35)

ωres = ωr2o − 14 (ŴN − Ŵs )2 . (36)

Thus, the actual oscillation frequency is given not by Eq. (34) but by Eq. (36). Often

(but not always!) we deal with γr o ≪ ωr o , so that ωres ≈ ωr o . Note that close to

threshold the oscillation can become overdamped when γr o > ωr o .

In conventional lasers the contribution of the photonic damping Ŵs to the relax-

ation oscillation damping γr o is usually very small, i.e., Ŵs ≪ ŴN . When a laser is

made very small, the photonic damping may become important (see Sect. VIII).

Thus “small” lasers are not only distinct from “large” lasers by a greater promi-

nence of the relaxation oscillation but also by a different nature of the damping of

the relaxation oscillation. In the limit of a thresholdless laser (β = 1) the relaxation

oscillation must disappear since, in the absence of a threshold, pump energy is con-

verted directly to laser output, without intermediate storage in the gain medium

(Yokoyama and Brorson, 1989). Another way to appreciate this is that the relax-

ation oscillation has a 90◦ phase shift between photons and atoms, i.e., total energy

is not conserved, whereas β = 1 implies energy conservation with respect to the

photon/atom balance (180◦ phase shift).

The amplitude spectrum s(ω) of the intensity noise can be obtained by Fourier

transformation of Eq. (30), leading to

[γ (1 + βs0 ) − iω] f s (ω) + γ βs0 f N (ω)

s(ω) = . (37)

ωr2o + ŴN Ŵs − ω2 − 2iωγr o

should reduce to class A; using d/dt = −iω ≈ 0 and Eq. (36), we find

γ (1 + βs0 ) f s (ω) + γ βs0 f N (ω)

s(ω ≈ 0) = . (38)

2κγ βs0 + ŴN Ŵs

expand Eq. (37) around ω ≈ ωr o , where the denominator has a minimum. For these

high frequencies the prefactor in front of f s (ω) by far outweighs the prefactor in

QUANTUM NOISE OF SMALL LASERS 225

front of f N (ω). In that case we can neglect the inversion noise, and integrate only

the −iω f s part of the noise power over frequency to find

+∞

1

dω Ŵs

|s(ω)|2 ≈ | f s (ω)|2
= s02 , (39)

−∞ 2π 4γr o Ŵs + ŴN

Also for low frequencies (ω ≪ ωr o ), it is allowed to neglect the inversion noise

f N (t) if we remain relatively close to threshold so that spontaneous-emission

noise dominates, i.e., βs0 ≪ 1. An experimental example of this latter case is

shown by the solid circles in Fig. 9, for a small (L ≈ 10 cm) HeXe 3.51-μm

laser oscillating in a single mode. We have plotted the power spectrum of the low-

frequency intensity noise versus the steady-state photon number (s0 ) in the cavity.

The fitted curve represents Eq. (38) with f N ≡ 0, taking into account corrections

for the bad-cavity effect (see Sect. III) and the nonideal nature of the Xe 3.51-μm

four-level scheme. This leads to the expression (van Eijkelenborg, 1998)

s0 2

|s(ω ≈ 0)| 2

≈

2

s0

sthr

+ , (40)

κβ s0 sthr

FIG. 9. Intensity-noise strength at low frequency versus the number of photons s0 in the laser cavity;

σ ≡ s − s0 stands for a small excursion of the photon number. We show results for both the stable

cavity (filled circles) and unstable cavity (open circles). The dashed curves are fits to Eq. (40), which

yields the threshold photon number sth for each case. We find sth = 858 ± 60 for the stable-cavity

laser (filled circles) and sth = (15.9 ± 1.5) × 103 for the unstable-cavity laser (open circles). (From

van Eijkelenborg et al., 1998, copyright 1998 APS.)

226 J. P. Woerdman et al.

FIG. 10. Spectrum of a Hitachi HLP1400 AlGaAs semiconductor laser operating at a total output

power of 3.2 mW. The spectrum was obtained by heterodyning the laser output with a tunable local

oscillator. Plotted is the spectral intensity versus the frequency of the local oscillator. In (a) the central

line is fitted to a Lorentzian curve with a HWHM of 34 MHz; (b) gives a different representation of the

same data showing the side bands resulting from relaxation oscillations. (From van Exter et al., 1992,

copyright 1992 IEEE.)

QUANTUM NOISE OF SMALL LASERS 227

with sthr as the photon number precisely at threshold (M = 1), sthr ∝ β −1/2 with a

prefactor of order unity.

The inversion noise f N plays an important role only high above threshold, when

it dominates the low-frequency intensity fluctuations. When the inversion noise is

suppressed, by using a quiet pump source, the low-frequency intensity fluctuations

disappear completely (“intensity noise squeezing”; see Lathi and Yamamoto, 1999,

and references therein). We will come back to this issue in Sect. IX.

Relaxation oscillations appear not only in the intensity–noise spectrum but also

in the field–noise spectrum, i.e., the optical spectrum of the laser. In this case

a theoretical description starts again from the Maxwell–Bloch equations, which

are now reduced to rate equations for the field E and the inversion N (instead of

s and N ). Amplitude modulation of the field E by the relaxation oscillation then

leads to sidebands spaced by ωr o from the central laser frequency; in the linearized

description there are two (weak) sidebands, on either side of the laser frequency.

An experimental example is shown in Fig. 10, for a semiconductor diode laser;

in such a laser the relaxation-oscillation sidebands have typically a strength of

∼1% of the central carrier; see Fig. 10b. Interestingly, the two sidebands have

different strengths. This is due to the fact that the oscillating inversion leads not

only to amplitude modulation (AM) but also to phase or frequency modulation

(FM) of the field. In fact, FM modulation occurs when there is a detuning of the

cavity mode and the gain profile [α = 0 in Eq. (13)]. The AM and FM modulation

interfere constructively in the red sideband and destructively in the blue side-

band. A semiconductor laser is effectively detuned, since its spectral gain curve is

asymmetric.

Semiclassical relaxation oscillations must somehow transform into one-photon,

one-atom Rabi oscillations when the laser device is reduced to a single atom

interacting with a single field mode. It is interesting to speculate on the na-

ture of this route. It seems likely that the concept of collective Rabi oscillation

(see Zhu et al., 1990; Brecha et al., 1995) is the link between the √ two limiting

cases. In this intermediate regime the dipolar

√ coupling is given by g N , leading

to a well-resolved Rabi oscillation if g N > κ, γ⊥ . In a linearized description

this is expected to correspond to the semiclassical relaxation oscillation; we are

presently studying the nature of the transition.

As argued in Sect. VII, the relaxation oscillation becomes stronger when a laser is

miniaturized; therefore, at some point, we will violate the linearization condition

s ≪ s0 . The onset of this breakdown can be predicted with the linearized theory

as presented in Sect. VII; we follow here the treatment by van Druten et al. (2000).

228 J. P. Woerdman et al.

s 2
ωr2o

ŴN

=1− ≡ 1 − (B)(A), (41)

s02 ŴN + Ŵs ωr2o + ŴN Ŵs

where we have introduced the factors A and B for easy reference. Equation (41) is

related to the second-order reduced factorial moment Q 2 and the Fano factor F of

the photon distribution,

= Q2 = 2

≈ , (42)

s0 s0 s02

difference between s0 and s0 + 1. The Fano factor normalizes the intensity fluc-

tuations to the shot-noise level, F = 1 for a Poissonian distribution. The reduced

factorial moment Q 2 normalizes the intensity fluctuations to those in a single

mode of a thermal field. For example, Q 2 = 1 for the Planck distribution in a

single optical mode, while Q 2 = 0 for a Poissonian distribution.

Although Eq. (41) has been derived for a class-B laser, it can be reduced to

recover the well-known result for a class-A laser by using Ŵs ≪ ŴN , i.e., B ≈ 1 in

Eq. (41); the behavior of Q 2 is then determined by the factor A ≤ 1 in Eq. (41),

M 1

Q2 ≈ , (43)

M − 1 s0

where we assumed that s0 ≫ β −1/2 . Thus, for a class-A laser, Q 2 ≈ 0 above thresh-

old, approaching the shot-noise limit (1/s0 ) for M → ∞. In fact, if we pass through

the threshold of a class-A laser from below, Q 2 jumps from ∼1 to ∼0 in an M in-

terval around M = 1 of order β 1/2 ; equivalently, the Fano factor F peaks at M = 1

at a value Fmax ≈ 21 β −1/2 , the width of the peak being of order β 1/2 (Rice and

Carmichael, 1994). Figure 11 illustrates this behavior of Q 2 and F as a function

of the pumping parameter M in a conventional (i.e., class-A) laser.

The appeal of Eq. (41) is that it shows directly that the noise level only drops

appreciably below the thermal level Q 2 = 1 when two conditions are met, namely,

A → 1 and B → 1. For a class-B laser we still have A ≤ 1 in Eq. (41), but now

also the possibility B < 1 arises, namely, when the photonic damping exceeds the

inversion damping, Ŵs > ŴN . Using Eqs. (31) and (32), this condition translates

into

QUANTUM NOISE OF SMALL LASERS 229

FIG. 11. Steady-state photon number s0 , second-order moment Q 2 , and Fano factor F of a conven-

tional laser (i.e., class A) as a function of the pumping parameter M.

Ŵc

= , (45)

γ

and assume, as before, the good-cavity regime. Thus, for a class-B laser (i.e.,

≫ 1), the possibility arises that the photon statistics remains thermal (Q 2 ≈ 1)

until far above threshold, as long as Eq. (44) is satisfied [here we assume that

the linearized Eq. (30), which is the basis of our analysis, remains approximately

valid]. Correspondingly, the peak in the Fano factor may shift far beyond M = 1.

We can now associate the threshold with either the kink in the steady-state output

[see Eq. (3)] or with the peak in the Fano factor. For a class-A laser the two

definitions coincide and are both governed by β. For a class-B laser, however, the

steady-state threshold is governed by β and the fluctuation threshold by β and ;

230 J. P. Woerdman et al.

FIG. 12. The solid curve shows the Fano factor F versus pump parameter M for a class-B laser with

β = 10−5 and = 102 ; see Eq. (45) for the definition of . For comparison, the dashed curve shows

the Fano factor of a class-A laser with the same β.

the spontaneous emission events in the lasing mode (at a rate κ) now build up

during the damping time of the relaxation oscillation (∼γ−1 ), yielding a much

more pronounced effect on the intracavity intensity. This integration effectively

increases the fraction of spontaneous emission in the laser mode from β into β,

as far as the fluctuations of the intracavity intensity are concerned.

The behavior of the Fano factor of a class-B laser is easily derived from Eqs. (41)

and (42). The Fano peak acquires a width of order (β)1/2 and occurs at M ≈ 1 +

(β)1/2 . This behavior of the Fano factor is illustrated in Fig. 12 for the case β =

10−5 and = 102 , i.e., β = 10−3 . For β ≫ 1 the laser becomes effectively

thresholdless as far as the intensity fluctuations are concerned; i.e., the inversion

decay into the nonlasing modes has negligible effect upon the fluctuation dynamics.

Note that the fluctuation threshold as discussed in this section refers to the

frequency-integrated noise [cf. Eq. (42)]. This is to be contrasted with the low-

frequency noise as given by Eq. (40) (see also Fig. 9). In the low-frequency limit

there is no distinction between a class-A and a class-B laser and the only thresh-

old parameter is β. As a consequence, when studying the two thresholds of a

class-B laser we may either compare the steady-state threshold with the frequency-

integrated fluctuation threshold, or we may compare the low-frequency fluctuation

threshold with the frequency-integrated fluctuation threshold.

The nature of the fluctuation threshold depends thus not only on the class-A

versus class-B nature (i.e., the value of ), but also on the value of β. This has

been illustrated in the phase diagram of Fig. 13. The macroscopic regime cor-

responds to class-A threshold behavior, characterized by a width β 1/2 . In this

case the atomic damping dominates over the photonic damping, even around the

steady-state threshold. For β > −2 we enter into a region where the photonic

damping exceeds the atomic damping, but in a narrow range above the steady-state

threshold only. The noise threshold is then broadened (but still relatively sharp).

QUANTUM NOISE OF SMALL LASERS 231

FIG. 13. Schematic display of the various regimes of the fluctuation threshold of a laser. The

parameter is defined by Eq. (45). The solid lines correspond to β = −2 and β = −1 . In

the macroscopic regime the spontaneous emission-driven relaxation oscillation is strongly damped,

in the mesoscopic regime the relaxation oscillation is present but is relatively weak, and in the mi-

croscopic regime it is completely dominating (100% modulation depth). The arrows indicate possible

routes toward a β = 1 laser. (Adapted from van Druten et al., 2000, copyright 2000 APS.)

Following Hofmann and Hess (2000), and in the spirit of the theme of this chapter,

we call this the mesoscopic regime. Finally, for β > −1 the photonic damp-

ing exceeds the atomic damping until far above threshold, so that the intensity

fluctuations have effectively become thresholdless. This may be called the micro-

scopic regime. In this regime the Fano peak has a width of order unity and a peak

value Fmax ≈ (/4β)1/2 . The arrows in Fig. 13 illustrate that one may reach the

fully thresholdless regime β = 1 either directly, always staying in the macroscopic

regime, or via the mesoscopic and microscopic regimes, where the fluctuation

threshold disappears first. The latter route seems more relevant, since small lasers

tend to be class B in the first place.

So far we have concentrated on the regime β ≪ 1, where a semiclassical treat-

ment is sufficient. This means that the extension toward β = 1 of the different

regimes in Fig. 3 is an extrapolation. The validity of this extrapolation will have

to be verified by a more rigorous (quantum) theory. In this regard it is interesting

that from a quantum birth–death model for a β = 1 laser with > 1, Rice and

Carmichael (1994) numerically find scaling laws that closely resemble our analyt-

ical results, strongly suggesting that the extrapolation of our results toward β = 1

is meaningful. For instance, for β = 1 they find Fmax ≈ 0.61/2 at s0 ≈ 1.61/2

(see the discussion of Fig. 8b in their paper, where λ ≡ ), directly analogous to

our results in the microscopic regime Fmax = 21 1/2 at s0 = 1/2 for β = 1).

Surprisingly, the condition β > 1 for thresholdless intensity fluctuations can

be simply rewritten in cavity QED terminology. By using Eq. (25) we can rewrite

232 J. P. Woerdman et al.

FIG. 14. Nd3+ microlaser (not to scale). The laser cavity is formed by the concave surface of the

output coupler and the pump-side surface of the Nd:YVO4 laser crystal. The (optical) cavity length is

∼0.5 mm. The dielectric coatings are indicated, HR for highly reflective, AR for antireflection coating.

(From van Druten et al., 2000, copyright 2000 APS.)

Eq. (44) as a condition on the atom-field coupling g, i.e., g > γ . Thus, the thresh-

oldless nature of the intensity fluctuations can be seen as some kind of remnant of

the vacuum Rabi oscillations of cavity QED; purely weak coupling would imply

that g is smaller than all other relaxation rates, i.e., also g < γ . Presently we are

studying the nature of this connection.

We have performed an experiment on a Nd3+ :YVO4 microlaser to investigate

these issues (van Druten et al., 2000). The configuration of the microlaser cavity is

shown in Fig. 14 and the essence of its level scheme has already been displayed in

Fig. 1. As a complication, the Nd3+ ion does not have an ideal four-level structure,

i.e., the decay rate of the lower laser level, γb , is not larger than the cavity decay

rate Ŵc , although it is very much larger than the decay rate of the upper laser

level (in fact, γb = 1.6 × 109 s−1 , γ = 1.3 × 104 s−1 , and Ŵc = 7 × 1010 s−1 ).

As a consequence, the inversion damping is not given by Eq. (32), but by (see van

Druten et al., 2000; Becher and Boller, 1999; Böhm et al., 1999)

Ŵc

ŴN = γ M + γ (M − 1) , (46)

γb

the response rate of the inversion becomes faster than γ M even if the lower laser

level is hardly populated, since the response of the population of the lower level

is very much faster than that of the upper level, γb ≫ γ . Equivalently, the second

term in Eq. (46) can be seen as a form of “nonlinear gain” or “gain compression,”

a well-known concept in the context of semiconductor laser physics (Becher and

Boller, 1999).

As shown in Fig. 15a, our Nd3+ :YVO4 laser has a sharp steady-state thresh-

old from which we deduce its β value, β = 7 × 10−6 . From the measured

QUANTUM NOISE OF SMALL LASERS 233

FIG. 15. Diagnostics of Nd3+ microchip laser. (a) Intracavity photon number s0 versus pumping

parameter M; the inset gives a blow-up of the threshold region. (b) Relaxation oscillating frequency

ωr o versus pumping parameter M. (Adapted from van Druten et al., 2000).

Ŵc = 7 × 1010 s−1 . Using Eqs. (31) and (46), we predict that the point ŴN = Ŵs is

reached around M ≈ 2, so the intensity fluctuations should be thermal for M ≤ 2.

This is illustrated in Fig. 16, which shows experimental time traces of the out-

put intensity for M = 6.6, M = 1.9, and M = 1.03. A reasonably stable output

with a modest relaxation oscillation (see Fig. 16a) changes into a strong, anhar-

monic relaxation oscillation (see Fig. 16c) and then into a highly irregular output

(see Fig. 16e). Note that M = 1.03 is still clearly above the steady-state threshold,

since β = 7 × 10−6 . We emphasize that these time traces are not chaotic; they cor-

respond to damped relaxation oscillations, continuously excited by spontaneous

emission (technical noise is negligible at these time scales). Chaotic time depen-

dence requires three independent variables instead of the two that we have here

(intensity and inversion); see Arecchi (1987). Figures 16b, 16d, and 16f show the

corresponding frequency spectra of the output intensity; higher harmonics of the

relaxation-oscillation appear and blend into a structureless continuum.

The experimental results for Q 2 versus M are illustrated in Fig. 17; instead

of a step function at M = 1, we observe the expected gradual decrease. In this

regime the inversion dynamics are incapable of stabilizing the laser output, which

is then very similar to that of a subthreshold oscillator. Surprisingly, the linearized

Eq. (41), plotted as the solid curve, gives a quite good representation of the data,

hardly worse than the numerical solution of the nonlinearized theory (dashed

curve).

234 J. P. Woerdman et al.

FIG. 16. Typical experimental time traces (left) and RF spectra (right, solid lines) of the output of

the Nd3+ microlaser, for different pump parameters M (a), (b): M = 6.6; (c), (d): M = 1.9; (e), (f):

M = 1.03. The RF spectra are normalized to the average output power, to yield the relative intensity

noise (RIN). The dashed lines in the spectra are the result of numerical integration of the laser Maxwell–

Bloch equations. (From van Druten et al., 2000, copyright 2000 APS.)

QUANTUM NOISE OF SMALL LASERS 235

FIG. 17. Second-order moment Q 2 of intensity fluctuations [see Eq. (42)] of Nd3+ microlaser versus

pump parameter M. The dots are experimental data, the full curve represents the linearized analytical

theory [Eq. (41)], and the dashed curve results from numerical integration of the laser Maxwell–Bloch

equations. The inset gives the same data but now expressed in the Fano factor F [see Eq. (42)]. (Adapted

from van Druten et al., 2000, copyright 2000 APS.)

Also very interesting is the shape of the photon distribution function; Fig. 18

shows an example for M = 7.28. Although the average photon number in this

experiment is as large as s0 = 4.1 × 105 , the distribution function has the shape of

a Poisson distribution with s0 ≈ 27. This corresponds again to the “fluctuation β”

of this laser being much larger than the conventional β, in this case by a factor

of 104 . For smaller M values the Poisson distribution in Fig. 18 develops in an

approximately exponential (thermal) distribution; see Fig. 19.

The good agreement between our experimental, theoretical, and numerical re-

sults shows that the linearized semiclassical treatment is surprisingly robust, even

when the fluctuations in intensity become comparable to the average. The latter is

by definition the case when Q 2 ≈ 1, i.e., precisely in the regime of interest. Never-

theless, the linearized theory must break down somewhere along the route to larger

values of β; at present β ≈ 1 has been achieved experimentally (van Druten

FIG. 18. Photon-number distribution of Nd3+ microlaser for a pump parameter M = 7.28. The

average photon number is s0 ≈ 4.1 × 105 . However, the shape of the photon distribution is that of a

Poissonian with on average only ∼27 photons in the mode. (Adapted from Lien et al., 2000, copyright

2000 APS.)

236 J. P. Woerdman et al.

FIG. 19. Photon-number distribution of Nd3+ microlaser for a pump parameter M = 1.04. The

fit curve is close to an exponential, showing the almost thermal nature of the laser emission above

threshold. (Adapted from Lien et al., 2000, copyright 2000 APS.)

et al., 2000), but β ≈ 10 seems feasible. One may still profit from linearization

of inversion excursions, N ≪ N0 , even when linearization of the photon num-

ber excursions (s ≪ s0 ) is no longer allowed. By separation of the time scale of

the relaxation oscillation itself and that of its slowly varying amplitude, one can

pursue analytical solutions farther into the nonlinear regime; this corresponds to

the concept of “quasi-energy” (Paoli et al., 1988).

Are there also other lasers besides Nd3+ microlasers where these phenomena

occur? It is interesting to have a look at semiconductor lasers; see also Hofmann and

Hess (2000), where the same issue is addressed. For an edge-emitting semiconduc-

tor laser one has typically β ≈ 10−5 and = Ŵc /γ = 1011 s−1 /109 s−1 ≈ 102 ;

thus β ≈ 10−3 , so the Fano peak should become asymmetric and wider by a factor

1/2 = 10 times wider than the steady-state threshold region (cf. Fig. 12). For a rea-

sonably small oxide-confined VCSEL one has a larger β, namely, β ≈ 10−3 (Shin

et al., 1997); however, one has the same value of = Ŵc /γ , namely, ∼102 , so the

relative increase in the Fano peak width is again a factor of 10. Verification of this

effect requires careful experimentation and in particular the exclusion of spurious

side effects; to our knowledge such an experiment has not yet been reported.

The quantum noise of a laser depends on (among other things) the cold cavity

loss rate Ŵc , either directly [cf. Eq. (11)] or indirectly [cf. Eq. (41)], with expres-

sions for ŴN , Ŵs , and ωr o substituted in these equations. It has been pointed out by

Petermann (1979) that there is a catch to this: different cavity configurations with

the same loss rate κ can lead to very different quantum noise. Siegman (1989)

QUANTUM NOISE OF SMALL LASERS 237

has shown that the most universal explanation for this is that the eigenmodes of

the cavity may become nonorthogonal due to loss; the eigenmode with the lowest

loss is the “lasing” eigenmode. The nonorthogonality of the cavity eigenmodes

causes noise in the other modes to project into the lasing mode. Petermann excess

noise is thus intrinsically a multimode phenomenon; in practice, however, it oc-

curs in cases that are usually labeled as “single-mode,” since the intensity in the

lasing mode greatly exceeds that in the other modes. Although loss is essential,

the degree of nonorthogonality is not at all uniquely determined by the value of

the round-trip loss (=round-trip gain), but instead by spatial inhomogeneity of

loss or gain in the cavity, and the same therefore applies to the quantum noise

of the laser output. Nonorthogonality due to spatial inhomogeneity may refer to

transverse eigenmodes (Petermann, 1979; Siegman, 1989) or longitudinal eigen-

modes (Hamel and Woerdman, 1989, 1990). Nonorthogonality may also occur

in polarization eigenmodes (van der Lee et al., 1997); in that case it is due to

polarization inhomogeneity (i.e., polarization anisotropy) of the laser cavity. The

equations used so far in this chapter assumed implicitly eigenmode orthogonality;

in the present section we will develop some feeling when and how this must be

generalized. For completeness we note that the K factor is an important concept

for any open quantum system, not just a laser. It arises in the general theory of

scattering resonances, where it enhances the scattering strength of a quasi-bound

state embedded in a continuum (see Frahm et al., 2000).

A first example is a laser based on an unstable cavity. In spite of its name, an

unstable-cavity laser is a perfectly bona-fide laser that can be easily made to emit at a

single frequency in a single spatial mode. In fact, the modal discrimination is much

better than in stable-cavity lasers. A typical example of an unstable-cavity laser is a

Fabry–Perot laser consisting of two convex mirrors (Siegman, 1986); a distributed

variety thereof has two plane mirrors with an index-antiguiding waveguide

between (Petermann, 1979).

The transverse eigenmodes of an unstable resonator are nonorthogonal. This

increases the spontaneous emission by the Petermann excess noise factor K; i.e.,

in a semiclassical treatment β is replaced by Kβ, with K ≥ 1, each eigenmode

having its own K factor (Siegman, 1989). Due to the mode nonorthogonality, the

(enhanced) spontaneous emission in the various eigenmodes is correlated in such

a way that the total spontaneous output of the device is not affected (Haus and

Kawakami, 1985); this is to be expected in view of the fluctuation-dissipation

theorem. Above threshold, however, the laser mode is much stronger than all other

modes, so that its K-factor survives. The value of this K factor depends on the

cavity geometry; for a mirror-based unstable cavity it depends on the transverse

magnification and the Fresnel number. Usually, K has to be calculated numerically;

analytical solutions are available when the mirrors have a Gaussian reflectivity

profile (Doumont et al., 1985).

238 J. P. Woerdman et al.

K values as high as 500 have been measured, and K ≈ 104 looks feasible in

a practical cavity (Cheng et al., 1996; van Eijkelenborg et al., 1996; van der Lee

et al., 1997, 2000a; Karman et al., 1998). Since Kβ > 1 seems within reach in a

reasonably small laser (β > 10−4 ), the question arises whether this implies some

form of thresholdless lasing (see below).

Petermann excess noise can be included in the laser rate equations, e.g., Eqs. (1)

and (2), in a heuristic way. We assume that the atoms in the gain medium have

p = β −1 photon-emission channels available for spontaneous emission. We simply

account for possible mode nonorthogonality by giving one of the photon emission

channels, i.e., the lasing mode, a K-times higher weight than the others. Note that

this weight factor applies only to the spontaneous emission rate into the lasing

mode, not to the stimulated emission rate. This recipe leaves Eqs. (1) and (2)

unchanged apart from replacing (s + 1) in Eq. (1) by (s + K ), i.e., it is as if there

are K noise photons in the laser mode instead of the usual 1. This result can also be

derived more rigorously from the Maxwell–Bloch equations (Dutra et al., 1999).

Since in our model Kβ takes the place of β, we have to assume Kβ ≪ 1, similar

to the assumption β ≪ 1 required for the validity of Eqs. (1) and (2).

Almost all work so far on the K factor has dealt with its effect on the phase

noise. The optical laser linewidth, as given by Eq. (11), is simply multiplied by K,

κ Ŵc

ωℓ = K =K , (47)

s0 2s0

where we assume the good-cavity limit. Figure 20 shows an experimental result for

a small unstable HeXe 3.51-μm laser where K ≈ 200 was deduced from a mea-

surement of the optical linewidth (van Eijkelenborg et al., 1996). Figure 21 shows

an experimental result for the linewidth of a stable HeXe 3.51-μm laser where the

polarization modes have been made nonorthogonal by using intracavity polariza-

tion optics; the linewidth (i.e., K ) is seen to diverge when the polarization modes

become parallel (van der Lee et al., 2000a). This polarization variety of Petermann

excess noise is not fundamentally different from the transverse eigenmode variety;

it has the experimental advantage, however, that the degree of nonorthogonality

can be easily adjusted. A theoretical advantage is that it allows analytical theory,

since only two modes are involved.

Equation (47) has been derived and experimentally verified for the usual case

that ωℓ ≪ Ŵc , i.e., s0 ≫ K . For s0 ≤ K one expects that the cavity acts as a

linear spectral filter so that ωℓ ∼ Ŵc . Thus, Schawlow–Townes narrowing should

set in for s0 > K instead of s0 > 1. The same statements apply to the bad-cavity

limit when K is replaced by γ⊥ . These predictions have not yet been verified

experimentally.

The effect of the K factor on the laser intensity noise has been studied recently

(van Eijkelenborg et al., 1998). Theoretically, one finds from Eqs. (1) and (2), after

QUANTUM NOISE OF SMALL LASERS 239

FIG. 20. Resonance behavior of the Petermann excess noise factor of a HeXe 3.51-μm unstable-

cavity laser as a function of the equivalent Fresnel number Neq : (a) theoretical; (b) experimental. The

curves in (a) and (b) have been added to guide the eye. (From van Eijkelenborg et al., 1996, copyright

1996 APS.)

1

s0 = [(M − 1) + (M − 1)2 + 4M Kβ]. (48)

2β

Comparison with Eq. (3) shows that the abruptness of the threshold transition is

now governed by Kβ instead of β. This is illustrated in Fig. 22, which shows the

cases Kβ = 10−6 , 10−4 , and 10−2 . Theory for Kβ ≥ 1 is not available, but we

anticipate that the threshold in Fig. 22 will simply disappear, as it does in Fig. 3

for β → 1. This implies thresholdless lasing, but of a different nature than in

Fig. 3 since the threshold, when fading away in Fig. 22, does not move toward a

vanishing pump rate but stays at a fixed pump rate. In other words, thresholdless

lasing corresponding to Kβ > 1 is naturally inefficient, contrary to the β = 1

thresholdless laser, which has 100% efficiency.

240 J. P. Woerdman et al.

FIG. 21. Petermann excess noise factor in the optical linewidth of a HeXe 3.51-μm laser with

nonorthogonal polarization modes. The angle between the eigenpolarizations of the cavity is α. The

squares are experimental points at an output power of 9 μW. The dashed theoretical curve represents the

prediction of mode-nonorthogonality theory and the solid theoretical curve incorporates, apart from

the (linear) mode-nonorthogonality theory, the effect of saturation. (Adapted from van der Lee et al.,

2000a, copyright 2000 APS.)

shown in Fig. 9, in which we compare the low-frequency intensity noise of a

stable- and unstable-cavity HeXe 3.51-μm lasers. The peaks in Fig. 9 occur at the

respective thresholds; the peak positions are consistent with the values of Kβ for

the two lasers (van Eijkelenborg et al., 1998). Figure 23 shows the effect of the

K factor on the intensity noise of a HeXe 3.51-μm laser for the polarization variety

FIG. 22. Laser threshold characteristics in the presence of Petermann excess noise. The intracavity

photon number s0 is plotted versus the dimensionless pump parameter M. The drawn curves are

calculated from Eq. (48) using β = 10−6 and K = (a) 1, (b) 102 , and (c) 104 . The presence of excess

noise smoothens the input–output curve. (From van Eijkelenborg et al., 1998, copyright 1998 APS.)

QUANTUM NOISE OF SMALL LASERS 241

FIG. 23. Petermann excess noise factor in the low-frequency (0.5-MHz) intensity noise of a HeXe

3.51-μm laser with nonorthogonal polarization modes. The angle between the eigenpolarizations of

the cavity is α. The fit curve corresponds to mode-nonorthogonality theory. (Adapted from van der Lee

et al., 2000a, copyright 2000 APS.)

of Petermann excess noise; the noise strength diverges when the polarization modes

become parallel (van der Lee et al., 2000a).

The K factor has been shown to be frequency dependent due to the dynamics

of the gain medium. In other words, the excess quantum noise appearing in the

intensity noise spectrum is “colored” as opposed to true quantum noise, which

is “white.” This is illustrated in Fig. 24 (van der Lee et al., 1998). This spectral

coloring is often Overlooked, since one generally assumes one mode to dominate

FIG. 24. Coloring of the Petermann excess quantum noise, measured in the enhancement of the

intensity noise of a stable-cavity HeXe gas laser, for two different values of the nonorthogonality

of the polarization eigenmodes, i.e., two different values of cos α. The dashed curves are fits to the

experimental data. Note that the bandwidth of the coloring is smallest for the case of largest excess

noise factor. (Adapted from van der Lee et al., 1998, copyright 1998 APS.)

242 J. P. Woerdman et al.

over all others and thus neglects the dynamics of weak nonorthogonal side modes.

It is the correlated dynamics in these side modes that project into the measurement

direction and can thereby partially cancel the excess noise. These projections can

be relatively strong, as they correspond to a type of heterodyning and are therefore

first-order in the side-mode amplitude. Spectral coloring shows if one explicitly

takes into account the time dependence of all side modes and thereby proceeds

beyond the standard geometric picture of excess noise (van Exter et al., 2000).

The “nonorthogonality theory” of Petermann excess noise is a semiclassical

theory; it has the advantage of giving a very simple “geometric” description. It has

the disadvantage that it cannot be straightforwardly quantized, since the complex

amplitudes of a set of classical nonorthogonal modes cannot be turned into a set

of commuting operators. Grangier and Poizat (1998, 1999) have shown how this

problem can be circumvented by introducing appropriate “vacuum modes” that

allow one to recover the unitarity of the input–output scattering matrix.

Very recently, attention has been drawn to the fact that Petermann excess noise

may have disastrous effects on the intensity noise squeezing in a quietly pumped

semiconductor laser as discussed in Sect. VII (van der Lee et al., 2000b). The cru-

cial point is that nonorthogonality leads to effects in first order of the nonlasing-

mode amplitudes, in contrast to many multimode effects considered previously that

are second-order effects (Lathi and Yamamoto, 1999). Thus, mode nonorthogonal-

ity leads to homodyning of the noise of side modes into the lasing mode; this can

destroy squeezing even when the side modes are suppressed, intensity-wise, far

below the shot noise of the lasing mode. It can be shown that above a critical value

of the K factor (K crit = 32 ) the laser intensity noise cannot be brought below shot

noise even for perfectly quiet pumping. In real semiconductor lasers the existence

of mixed gain-index guiding leads to nonorthogonality of the transverse modes

and implies K > 1; the critical value of 23 may be easily exceeded, depending on

the details of the device architecture.

The value K crit = 32 may seem strange, since rarely in physics does a factor

3

2

appear. One must realize, however, that the number of “extra” noise photons

in the laser mode is K − 1. When this number is of the order of the shot noise,

i.e., K − 1 = O(1), one must expect that squeezing due to quiet pumping becomes

impossible, since quiet pumping affects only the “original” noise photon in the laser

mode and not the projected noise from the other modes. The actual calculation

gives K crit − 1 = 21 , where the “ 12 ” is due to the 3 dB extra noise above shot noise

associated with the (linear) phase-insensitive amplification of the nonlasing mode

(Haus and Mullen, 1962).

We now address the role of the number of atoms in the mode volume of a laser,

Nat , instead of the number of photons, s. The latter was continuously emphasized

QUANTUM NOISE OF SMALL LASERS 243

in the previous sections; as we have seen, all kind of deviations from the behavior

of a conventional laser may occur even if the photon number remains much larger

than unity.

Does a similar statement also hold for the atom number Nat ? In fact, it does,

namely, when Nat becomes of order Nthr , where Nthr is the threshold inversion

required for lasing, Nthr = Ŵc /βγ = β −1 in the good-cavity case. In the usual

laser theories it is assumed that Nat ≫ Nthr ; in that case the pumping process can

be considered as Poissonian and can be simply described by a pumping rate R

in the rate equation for the inversion [cf. Eq. (2)] (Protsenko et al., 1999). This

assumption is so common that it is hardly ever made explicit. Nevertheless, when

making a laser smaller and smaller, the condition Nat ≫ Nthr may break down.

This has been discussed (see Enomoto et al., 1996) in work on pulsed microcavity

dye lasers; it was pointed out that the S-shaped output–input curve (as shown in

Fig. 2) is greatly “softened” when the number of dye molecules in the mode volume

is only marginally larger than the required threshold inversion number. In other

words, a naively deduced β value based on this S curve would be far too large. This

issue has been addressed theoretically, studying the transition from Nat ≫ Nthr to

Nat ≪ Nthr (Koganov and Shuker, 1998). This analysis confirms that the threshold

indeed disappears for Nat = Nthr . Thus, we deal here with yet another variety of

the thresholdless laser.

In a cavity QED context (not dealing with lasers), the importance of the atom

number Nat and the photon number s is well known (Kimble, 1994). In that con-

text the so-called critical (or saturation) value of Nat is β −1 and the critical

(or saturation) value of s is given by scrit = β −1 . The emphasis is then on cases

where Nat ≈ β −1 ≈ 1 and s ≈ β −1 ≈ 1.

Experimentally, the situation that Nat ∼ Nthr can be realized with a

continuous-wave (CW) pumped Nd3+ :YVO4 microlaser, which has [Nd3+ ] =

Nat ≈ 1 × 1020 cm−3 . Can all Nd3+ ions (in the mode volume) be indeed inverted,

using a practical pump, in this case a Ti:Sa laser at 809 nm? This requires that

the pump intensity is much larger than the saturation intensity of the pump transi-

tion. Based on the absorption coefficient of Nd3+ :YVO4 of 31 cm−1 at the pump

laser wavelength and an upper-level lifetime of 90 μs (data taken from the Casix

Crystal Guide 1997/1998), we estimate the saturation intensity as 104 W/cm2 .

Full inversion requires then, say, 105 W/cm2 as pump intensity, e.g., 100 mW in a

10-μm-diameter pump spot, which is feasible. Assuming full inversion and using

a stimulated-emission cross section of 2.5 × 10−18 cm2 , we calculate a gain co-

efficient of 2.5%/μm. Therefore a fully inverted Nd3+ :YVO4 microlaser with a

chip thickness of 40 μm and a mirror-reflectivity product of R1 R2 = e−2 satisfies

the criterion Nat = Nthr .

It is straightforward to estimate Nthr for the general case (i.e., beyond the nu-

merical example given above). We have Nthr = Ŵc /βγ = β −1 in the good-cavity

case. We conclude that finite-atom-number effects will occur when the atom num-

ber is reduced to roughly β −1 . It would be very interesting to study the fluctuation

244 J. P. Woerdman et al.

FIG. 25. Level scheme of a laser with emphasis on the recycling of the active atoms (cf. Fig. 1).

theory for these nonclassical fluctuation aspects does not seem to be available.

The finite-atom-number effect discussed here must not be confused with another

effect, namely, intensity noise squeezing due to depletion of the atomic ground

state by the pump (Hart and Kennedy, 1991; Ritsch and Zoller, 1992; Koganov

and Shuker, 1999). This effect is a consequence of the conservation law of level

populations in a single atom, i Ni = 1 (in contrast, the finite-atom-number effect

is based on the conservation law for the total number of atoms). The dynamical

recycling of the active laser atoms to the upper laser level after having emitted

a laser photon (see Fig. 25) leads to intensity noise squeezing. This condition

requires in practice impossibly high pump parameters, e.g., M > 105 in case of

a Nd3+ :YVO4 laser. Kolobov et al. (1993) also discovered this noise suppression

due to dynamical recycling.

We have discussed the various aspects that appear when a laser is made “small.”

What counts is not the physical size of the device, but the number ( p) of degrees

of freedom of the optical field. This leads to the spontaneous emission factor

β (= p −1 ); this is the key geometric parameter that characterizes the threshold

behavior of the laser. For a conventional (i.e., “class-A”) laser, the variables of the

gain medium are slaved to the cavity field and β is easily calculated. When the

size of a laser is reduced, the variables of the gain medium become increasingly

independent. Particularly relevant then is the case that the inversion decay rate

is much smaller than the cavity decay rate (“class-B” laser) and/or the case that

the cavity decay rate is much larger than the gain linewidth (“bad-cavity” laser).

For these cases, apart from β, also another dimensionless parameter, this time

associated with the gain medium, determines the threshold behavior. This is γ⊥ /κ

for a bad-cavity laser [cf. Eq. (25)], or = Ŵc /γ = 2κ/γ for a class-B laser

[cf. Eq. (45)], or Ŵc /γb for a nonideal four-level laser [cf. Eq. (46)].

QUANTUM NOISE OF SMALL LASERS 245

Small lasers, even when emitting in a single spatial mode, are much less coherent

than large lasers. For the case of a class-B laser this is associated with the fact that

the spontaneous emission-driven relaxation oscillation becomes very strong. As

a function of pump rate, the average output intensity shows a sharp threshold,

but the intensity fluctuations do not. Under quite generic conditions the intensity

fluctuations of a microlaser may show highly super-Poissonian statistics, due to

the very weak damping of the spontaneous emission-driven relaxation oscillation.

This classification corresponds to the mesoscopic and microscopic regimes

in the phase diagram of Fig. 13. It should be pointed out that the distinction

between these regimes is not identical to the distinction between class-A and class-

B lasers. The latter distinction is based purely on (=Ŵc /γ ); < 1 for class-A

lasers and > 1 for class-B lasers. Whereas class-A lasers always operate in

the conventional, “macroscopic” regime, class-B lasers may operate in any of the

three regimes, depending on the value of β. The current trend toward smaller laser

devices leads to lasers with increased β and ( increases because typically γ is

a material property of the gain medium, while κ increases with decreasing cavity

length). Thus, this trend will naturally lead to lasers that have “mesoscopic” or

even “microscopic” intensity fluctuations.

From the point of view of applications, it is not necessarily a disadvantage that a

small laser is naturally noisy/incoherent. On the contrary, for optical recording and

reading, an incoherent light source is preferred, since it is much less susceptible to

noise due to (unavoidable) optical feedback. The light source has to emit, however,

in a single spatial mode, as is the case for the microlasers discussed in this chapter.

We have elucidated the role of Petermann excess noise due to mode non-

orthogonality; this may make a laser much noisier than would naively correspond

to its cavity loss rate. Particularly relevant is that this may impede intensity noise

squeezing in quietly pumped semiconductor lasers. Fully or partly gain-guided

laser devices are very unfavorable in this respect; this is unfortunate, since a cer-

tain amount of gain guiding is unavoidable in any efficient device since the gain

must be localized, i.e., must not extend beyond the volume of the oscillating mode.

As a unifying remark, Petermann excess noise can be seen as a consequence

of inhomogeneity of the laser device. Transverse spatial inhomogeneity results

from having a cavity with convex mirrors, or from waveguiding by an index or

gain profile; longitudinal spatial inhomogeneity results from strong outcoupling.

Both varieties may lead to excess noise (K > 1). Polarization inhomogeneity

results from polarization-dependent elements inside the cavity; this may also

lead to excess noise (K > 1). Finally, spectral inhomogeneity, in the form of a

detuning of the cavity mode and the gain peak, also leads to excess noise via the α

factor [cf. Eq. (13)]. Formally, the α factor can be seen as a variety of the K factor

(van Exter et al., 2000).

In the laser literature one finds much emphasis on the value of the photon num-

ber s in its route s = ∞ → s = 1. The importance of the atom number Nat in the

246 J. P. Woerdman et al.

similar route Nat = ∞ → Nat = 1 has only recently been appreciated in a laser

context, and the nonclassical consequences of the pump correlations imposed

by Nat ≈ Nthr ≫ 1, where Nthr is the threshold inversion, await experimental

verification.

We have encountered a variety of thresholdless lasers. Conditions for thresh-

oldless lasing are β = 1 (Sect. II), β ≫ 1 (Sect. VIII), Kβ ≫ 1 (Sect. IX) or

Nat = Nthr (Sect. X). It will be very interesting to study the fluctuation behavior

for these various cases, both theoretically and experimentally.

Finally, we come back to the common wisdom as expressed in the statements

1–3 in Sect. I. For small lasers these statements should be amended as follows:

1. For a small laser the threshold condition is gain < loss; the difference is

made up by spontaneous emission, which becomes increasingly important

for smaller lasers.

2. The laser linewidth depends also on the gain linewidth when the cavity

linewidth becomes larger than the gain linewidth (bad-cavity laser); this is a

natural situation for a sufficiently small laser.

3. The photon statistics of a sufficiently small class-B laser do not change when

the pump exceeds threshold due to strong relaxation oscillations, sufficiently

small being quantified by Eq. (44).

XII. Acknowledgments

We acknowledge the Foundation for Fundamental Research of Matter (FOM) and

the European Community (TMR Network Microlasers and Cavity QED) for fi-

nancial support. The research of NJvD was made possible by the Koninklijke

Nederlandse Akademie van Wetenschappen.

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Index

electron-scattering conditions in

Absorption rate coefficient, definition, 71 planar geometry, 170

Air Force Geophysical Laboratory general coordinate system in laboratory

(AFGL), spectral database, 156 frame of reference, 168

AlGaAs semiconductor laser magnetic angle changing technique, 173

inverse linewidth as function of total principles, 167–173

output power, 212 pulsed supersonically cooled target

spectrum, 226 beam, 176

Alkali dimers, long-range wells, 59 relationship between electron-scattering

Amplification, parametric, of atomic and angle and target recoil angle, 170–172

optical fields, 38–43 schematic of experimental apparatus at

Angular momentum operators, four-wave Manchester, 174

mixing, 31–32 supersonic expansion, 175

Anomalous density, finite temperatures, time-of-flight measurement, 176–177

21–22 time-of-flight spectrum from

Argon, high Rydberg spectrum, helium, 178

194, 195 velocity distribution of supersonically

Atomic deflection expanding gas beam, 175

advantage of measuring deflected target Atom optics

yield, 172–173 analogy with nonlinear optics, 2

comparing recoil cross-section and developments, 1–2

magnetic angle changing technique early experiments, 2

results, 181–182 Atoms, finite number, small laser, 242–244

conservation of energy and momentum, Aurorae

168–169 excited atmospheric species losing

DCS measurements exciting states of energy, 142–143

helium, 180 Galileo orbiter revolving around Jupiter

deflection angle as function of incident and satellites, 141

electron energy for helium, 172 giant planets, 139–143

deflection of helium as function of H+3 and H2 emission lines on Jupiter, 140

electron scattering angle, 171 pure rotational excitations of molecules

detector for exciting and deflecting by electrons, 142

targets, 176

differential cross section (DSC), 177

differential cross-section measurements, B

177–182

dual nature of reaction, 170, 171 Bad-cavity regime

experimental recoil techniques, laser, 211–214

173–177 spontaneous emission factor, 216–217

fitting Gaussian peaks to time-of-flight Ballistic expansion, temperature

spectra, 179 measurement, 95

249

250 INDEX

perturbations from static, 19–20 potential, 65

Bohr–Sommerfeld, quantization Chebyshev expansions, vibrational

condition, 66 wavefunctions, 107

Bose–Einstein condensates Cold atomic source, Orsay experiment,

contour and three-dimensional 80–83

gray-scale renditions, 18 Cold molecules

four-wave mixing, 28–29 applications, 54

See also Mean-field theory detection, 84, 85

efficient ways, 56

formation rate, 111–114

C helium buffer gas cooling technique, 56

laser cooling techniques, 55–56

Canada–France–Hawaii Telescope rapid evolution of field, 56

(CFHT), auroral images of Jupiter, 133 Stark decelerator, 36, 56

Cavity QED, spontaneous emission factor, See also Photoassociation; Ultracold

219–221 molecules

Cavity resonance, spectra, 216 Cold target recoil ion momentum

Centre National de la Recherche spectroscopy (COLTRIMS)

Scientifique (CNRS), spectral ionization experiment, 165

database, 156 See also Recoil techniques

Cesium Collective atomic recoil laser (CARL),

Cs+2 ion signal, 86 ultracold regime, 38–39

Cs+2 ion signal vs. detuning of Collisional processes, cometary spectra,

photoassociation laser, 90 154–155

demonstrating use of photoassociation, Comets

99–100 collisional processes for cometary

detection, 84, 85 spectra, 154–155

energy-normalized wavefunction for comparing best-fit model and tail

scattering of two ground-state atoms, spectrum, 148

75, 76 CSHELL/IRTF spectra of comet

experimental and theoretical Hale–Bopp, 150

photoassociation rates, 110 infrared spectra, 149–151

ion spectrum, 88–91 isotopic abundances, 153–154

level spacing, 68–69 producing atoms, molecules, radicals

optical pumping scheme, 55 and ions, 145

photoassociation spectra, 84–91 radio spectra, 151–155

potential curves for Hund’s case, 63 spectroscopy, 145–155

potential curves for interaction between ultraviolet and visible spectra, 146–149

two ground-state atoms, 59–60 visible range, 146, 147

short-range behavior of wavefunctions See also Giant planets and comets

for two levels, 65 Condensate density, finite temperatures, 21

time evolution of Cs+ 2 ion signal, 92 Condensate modes, quantifying quantum

translational temperature, 93–94 entanglement, 35–37

trap-loss spectrum, 85, 87–88

tunneling effect, 114–115, 116

ultracold molecules by photoassociation, D

79–80

vapor-loaded MOT, 81–82 Databases, spectral, and needed

vibrational wavefunction, 93 improvements, 155–156

INDEX 251

four-wave mixing, 23–37 measurements, 166

See also Nonlinear optics observations of momentum-analyzed

Differential cross section (DCS) doubly excited state fluorescence

electron excitation of target, 177 decay, 184–187

fitting Gaussian peaks to time-of-flight principles of deflection technique,

spectra from helium, 179 167–173

measurements for helium, 180 principles of doubly excited targets,

time-of-flight spectra for helium, 178 182–184

Doubly excited states principles of stepwise laser probing,

experimental techniques, 184 187–190

function extracted from time-of-flight recoil in crossed-beam interaction, 164

spectrum, 186 recoiling excited atoms, 182–187

observations of momentum-analyzed, results from laser probing of metastable

fluorescence decay products, 184–187 targets, 192–199

principles, 182–184 stepwise laser probing of deflected

time-of-flight of metastable atoms as metastable targets, 187–199

function of incident electron techniques producing well-defined target

energy, 186 momentum, 166–167

time-of-flight of metastable helium as threshold metastable excitation of

function of atom recoil angle, 185 helium, 166

time-of-flight of metastable atoms as

E function of incident electron

energy, 186

Electric dipole interaction, matter-light time of flight of metastable helium as

coupling, 13 function of atom recoil angle, 185

Electric dipole transition moments, need two-step laser process, 200–201

for accurate, 108–109 Electron impact. See Atomic deflection

Electron-excited targets Equation of motion, finite temperatures,

atomic deflection using electron impact, 21–22

167–182

cold target recoil ion momentum F

spectroscopy (COLTRIMS), 165

differential cross-section measurements, Finite-atom-number, small laser, 242–244

177–182 Finite temperatures, mean-field theory,

doubly excited state excitation function 20–23

from time-of-flight spectrum, 186 Fluctuation threshold

doubly excited states via fluorescence diagnostics of Nd3+ microchip

decay, 182–187 laser, 233

experimental recoil techniques, 173–177 disappearance for small lasers, 227–236

experimental techniques for doubly Fano factor versus pump parameter for

excited targets, 184 class-B laser, 230

experimental techniques of stepwise frequency-integrated noise, 230

laser probing, 190–192 nature depending on class-A vs. class-B

experiments exploiting internal energy nature and β value, 230–232

of metastable targets, 165–166 Nd3+ microlaser, 232

experiments studying, 163–164 photon-number distribution of Nd3+

future experiments, 199–221 microlaser, 235, 236

inelastic electron-scattering schematic of various regimes of,

process, 165 of laser, 231

252 INDEX

second-order moment of intensity stationary-phase method, 74

fluctuations of Nd3+ microlaser, 235

second-order reduced factorial moment G

and Fano factor of photon

distribution, 228 Galileo

steady-state photon number, carbon abundances in Jupiter, 136

second-order moment, and Fano isotope ratios by mass spectrometer

factor of conventional laser, 229 probe, 137

typical experimental time traces and RF revolving around Jupiter and its

spectra of Nd3+ microlaser, 234 satellites, 141

Fluorescence decay. See Doubly excited studying giant planets, 132

states Giant planets

Formation of molecules. See aurorae, 139–143

Photoassociation infrared spectra, 132–135

Four-wave mixing Jupiter, Saturn, Uranus, and

angular momentum operators, 31–32 Neptune, 131

Casimir operators, 32 molecular abundances from

Central-mode-side-mode correlation, 36 spectroscopic observations, 135–138

condensate wave function, 25 Titan, 143, 144

conservation of particle number, 30–31 ultraviolet and visible spectra, 132

dynamics of population exchange Giant planets and comets

between modes, 33–34 atmospheres, 130

evolution of population, 34 laboratory spectroscopic studies of

generation of fourth matter wave from visible region, 130–131

three initial waves, 28, 29 molecular emissions, 131

geometry, 30 spectral databases and improvements

Gross–Pitaevskii equation, 25 needed, 155–156

Hamiltonian, 30 spectroscopic observations, 130

illustration, 32–33 Goddard Space Flight Center (GSFC),

mean field analysis, 24–27 spectral database, 156

momentum and energy conservation Good-cavity regime

conditions, 26–27 laser, 211–214

original theory, 23–24 spontaneous emission factor, 216

population differences, 31 Gordon method, vibrational

possibility of obtaining quantum wavefunctions, 107

correlations between side modes, 35 Gross–Pitaevskii

quantifying quantum entanglement derivation, 15–19

between condensate modes, 35–36 energy functional, 17

quantum theory of atomic, 27–37 four-wave mixing, 25–26

scattering process, 27 nonlinear Schrödinger equation, 16

second-quantized Hamiltonian, 29 Ground state

side-mode-side-mode correlation, 37 formation of, molecules as short-range

spinor operators, 31 process, 69

time evolution of central mode-side making molecule, 78–80

mode correlation function, 36

two-mode correlation functions, 37 H

Franck–Condon factor

estimation of photoassociation Hale–Bopp

probability, 73 CSHELL/IRTF spectra, 150

INDEX 253

lines, 152 low-frequency, 241

radio spectra, 151–153 resonance behavior of Petermann excess

Hamiltonian noise factor, 239

four-wave mixing, 30 Hubble Space Telescope (HST), studying

Hartree–Fock–Bogoliubov, 22–23 giant planets, 132

manybody theory, 8–9 Hyakutake

manybody to N-particle state, 11 measured and modeled A–X (0–0)

parametric amplification of optical and bands of CH and CD, 153

matter waves, 39 radio spectra, 151–153

second-quantized for four-wave Hydrogen (H2), Rydberg state spectrum,

mixing, 29 196, 197

second-quantized with bosonic

commutation relations, 13 I

two-body collisions, 14, 15

Hartree–Fock–Bogoliubov Hamiltonian, Inelastic electron-scattering process,

finite temperatures, 22–23 exploiting initial target momentum, 165

Hartree wave functions, mean-field Infrared Interferometer Spectrometer and

theory, 15 Radiometer (IRIS)

Heisenberg equation of motion, manybody far-infrared spectra of Jupiter and

theory, 9–10 Saturn, 137–138

Helium Jupiter in 1979, 132

atomic deflection angle as function of molecular abundances from

incident electron energy, 172 spectroscopic observations,

deflection of metastable state, 171 135–138

differential cross-section Voyager IRIS spectrum from equatorial

measurements, 180 region of Jupiter, 135

doubly excited state function from Infrared Space Observatory (ISO)

time-of-flight spectrum, 186 Saturn and Neptune spectra, 132–133

field ionization and metastable signals in short-wavelength spectrometer, 133–134

upper detector, 198, 199 Infrared spectra

fitting Gaussian peaks to time-of-flight Canada–France–Hawaii Telescope

spectra, 179 (CFHT), 133

laser probing results, 192–193 comets, 149–151

momentum of metastable state, 171 far-infrared spectra of Jupiter and

threshold metastable excitation, 166 Saturn, 137–138

time-of-flight of metastable, as function giant planets, 132–135

of atom recoil angle, 185 Infrared Interferometer Spectrometer

time-of-flight of metastable atoms as and Radiometer (IRIS), 132–133

function of incident electron Infrared Space Observatory (ISO),

energy, 186 132–133

time-of-flight spectra, 178 Infrared Telescope Facility (IRTF), 133

Helium buffer gas, cooling local thermodynamic equilibrium (LTE)

technique, 56 approximation, 134–135

HeNe laser, linewidth-power product as near-infrared spectra of Neptune and

function of cavity decay rate, 213 Saturn, 139

HeXe laser strong emission of V3P branch of CH4

coloring of Petermann excess quantum on Jupiter, 134

noise, 241 Infrared Telescope Facility (IRTF), auroral

Petermann excess noise factor, 240 images of Jupiter, 133

254 INDEX

studying giant planets, 132 photoassociation, 80

Ion spectrum, photoassociation, 88–91 vapor-loaded, 81–82

Isotopic abundances, comets, 153–154 Magnitude, spontaneous emission factor,

221–222

Manybody theory

J applying manybody Hamiltonian to

Jet Propulsion Laboratory (JPL), spectral N-particle state, 11

database, 156 continuity equation for quantum field

Jupiter operators, 11–12

carbon abundances, 136 Hamiltonian, 8–9

far-infrared spectra, 137–138 Heisenberg equation of motion, 9–10

H+ matter-light coupling via electric dipole

3 and H2 emission lines over polar

haze of auroral region, 140 interaction, 13

Infrared Interferometer Spectrometer mode expansion of Schrödinger field

and Radiometer (IRIS), 132 operator, 12–13

strong emission of V3 P branch of multiparticle evolution, 11

CH4, 134 N-particle wave function in terms of

Voyager IRIS spectrum from equatorial Schrödinger field creation operator, 10

region, 135 nonlinear optics, 8–14

See also Giant planets Schrödinger wave function, 9

simple harmonic oscillator, 13–14

two-body collisions, 14

L Mapped Fourier method

calculation of kinetic energy

Laser cooling operator, 104

applications, 54 Fourier expansion, 105

photoassociation, 55–56 interpolated wavefunction in x

Laser probing. See Stepwise laser probing variable, 106

Lasers. See Quantum noise of small lasers maximum momentum, 102

LeRoy–Bernstein law radial Schrödinger equation,

bound levels, 64–70 103, 104

fit for trap-loss spectrum, 87 vibrational wavefunction for Cs2, 106

interpretation and fitting vibrational wavefunctions, 101–107

experiments, 70 Matter-light coupling, electric dipole

Local thermodynamic equilibrium (LTE), interaction, 13

radiative transfer calculations, 134–135 Matter-wave amplifier

Long-range external wells characteristic input-output, 50

alkali dimers, 59 phase-coherent, 49–50

dipole-dipole interaction, 63–64 Matter-wave superradiance

explanation for existence, 61 antinormally ordered characteristic

Luminorefrigeration, laser cooling, 54 function, 47

atomic field operator, 44

M closed atomic system, 46

coupling coefficients of Hamiltonian, 43

Magnetic angle changing technique deriving equation of motion, 45–46

atomic deflection, 173 generating families of higher-order side

comparison to recoil cross-section modes, 45

results, 181–182 geometric dependence of single-atom

Magnetooptical trap device (MOT) gain, 47–48

INDEX 255

number distribution for chaotic field, 47 accurate, 108–109

quantization of q values, 44–45 Molecules, formation. See

quasi-mode populations, 45 Photoassociation

single-atom gain, 48

superradiant matter-wave scattering, 44

unfair competition, 48–49 N

Mean-field theory 3+

Nd laser

anomalous Bose correlations, 20

diagnostics, 233

anomalous density, 21

photon-number distribution, 235, 236

Bose commutation relation, 16

schematic, 232

condensate density, 21

second-order moment of intensity

condensate wave function, 16

fluctuations, 235

deriving Gross–Pitaevskii equation,

typical experimental time traces and RF

15–19

spectra, 234

effective single-particle states, 15

See also Fluctuation threshold; Quantum

equation of motion for condensate

noise of small lasers

excitations, 21–22

Neptune

equation of motion for condensate wave

H2–H2 dimer features in near-infrared

function, 21

spectra, 139

finite temperatures, 20–23

Infrared Space Observatory (ISO),

four-wave mixing, 24–27

132–133

Gross–Pitaevskii energy functional, 17

See also Giant planets

Gross–Pitaevskii nonlinear Schrödinger

Nodal structure, zero-energy scattering

equation, 16

wavefunction, 75–77

Hartree–Fock–Bogoliubov Hamiltonian,

Noncondensate density, finite

22–23

temperatures, 21

Hartree wave functions, 15

Nonlinear optics

matter-wave four-wave mixing in

atom optics, 1–2

sodium Bose–Einstein condensate, 18

four-wave mixing of de Broglie waves,

noncondensate density, 21

23–37

order parameter, 16

manybody theory, 8–14

perturbations from static using

mean-field theory of Bose–Einstein

Bogoliubov quasi-particle approach,

condensates, 15–23

19–20

mixing of optical and matter waves,

self-consistent mean-field

37–50

approximation, 21

s-wave scattering, 3–8

Thomas–Fermi approximation, 19

Nonorthogonality theory, Petermann

total anomalous density, 22

excess noise, 242

total density, 22

Numerov approach, vibrational

zero temperature, 15–20

wavefunctions, 107

Mechanism, cold molecule formation,

91–92

Metastable atom recoil angular O

measurements, noble gases, 166

Metastable targets, experiments exploiting Optical and matter waves

internal energy, 165–166 atomic field initially consisting of

Molecular abundances, spectroscopic condensate below critical

observations, 135–138 temperature, 40–41

Molecular laser, proposal, 54 cross-correlation functions, 42–43

256 INDEX

effective atom-probe coupling analogy with Rydberg law, scaling law,

constant, 40 64–70

effective Hamiltonian, 39 approach using atomic physics

input-output characteristic of viewpoint, 72–73

matter-wave amplifier, 50 approximating potential matrix, 62–63

matter-wave superradiance, 43–49 approximations to simplify calculations,

mixing, 37–50 71–72

parametric amplification of atomic and Bohr–Sommerfeld quantization

optical fields, 38–43 condition, 66

phase-coherent matter-wave bottleneck in probability, 77

amplification, 49–50 C3 coefficient, 61

phase shift due to cross-phase calculations of overlap integrals, 77

modulation, 40 case of, into excited curve with

physics underlying parametric long-range behavior, 68

amplification, 38–39 choosing scattering lengths, 76–77

second-order equal-time intensity comparing experiment and theory for

correlation function, 42 rates, 109–111

two-mode correlations, 42 conservation of energy and angular

Optical pumping cycles momentum, 57

atomic cesium sample, 55 determining number of molecules in

cooling atoms, 54–55 experiment, 58–59

Orsay experiment dipole-dipole interaction dominating

cold atomic source, 80–83 long-range wells, 63–64

detection scheme, 85 effective quantum number, 67

experimental setup, 80–84 efficiency of reaction, 74–75

photoassociation laser, 83–84 energy-normalized wavefunction for

scattering of two ground-state Cs

P atoms, 75, 76

experiments, 57

Petermann excess quantum noise fine-structure effective operator, 61–62

coloring of, 241 formation of ground-state molecules in

dependence on cold cavity loss rate, short-range process, 69

236–237 formation of ultracold molecules, 56–57

effect of K factor on laser intensity Franck–Condon factor, 72

noise, 238–241 highly excited vibrational levels, 67–68

frequency dependence of K factor, ion spectrum, 88–91

241–242 laser cooling, 55–56

K factor, 237–238 LeRoy–Bernstein formula, 70

laser threshold characteristics in LeRoy–Bernstein law for bound levels,

presence of, 240 64–70

noise factor in low-frequency intensity level spacing, 74

noise of HeXe laser, 241 level spacing of Cs2, 68–69

nonorthogonality theory, 242 linking normalization factor to classical

Petermann excess noise factor in optical period of motion, 66–67

linewidth of HeXe laser, 240 local wavenumber and local de Broglie

resonance behavior of, of HeXe unstable wavelength, 66

cavity laser, 239 long range, 76–77

small lasers, 236–242 long-range alkali dimer molecules: pair

Photoassociation of atoms, 59–64

INDEX 257

magnetooptical trap device (MOT), 80 227–236

making molecule in ground state or finite number of atoms, 242–244

lower triplet state, 78–80 good-cavity vs. bad-cavity regime,

motion in potential with power-law 211–214

asymptotic behavior, 66 inverse linewidth of AlGaAs

new schemes for ultracold molecules, semiconductor laser as function of

116–117 total output power, 212

nodal structure of zero-energy scattering level scheme of laser, 207

wavefunction, 75–77 linewidth-power product of HeNe laser

orientation of dipoles, 61 as function of cavity decay rate, 213

overlap integral in semiclassical magnitude of β, 221–222

approach, 73–74 overview of threshold behavior, 207–210

potential curves for Hund’s case, 63 Petermann excess quantum noise,

potential curves for interaction between 236–242

two ground-state Cs atoms, 59–60 relaxation oscillation, 222–227

quantum formulation of transition spontaneous emission factor β, 214–219

between bound level and continuum, steady-state inversion number, 209

70–71 steady-state photon number as function

rate, 94–96 of pumping parameter for laser, 208

reflection principle for calculating steady-state photon number vs. pumping

Franck–Condon factors, 73–75 rate and cavity intensity decay

resonance condition, 58 rate, 209

short range, 77 Quantum theory, atomic four-wave mixing,

simple theory, 77–78 27–37

stationary-phase method for

Franck–Condon factor, 74 R

theoretical predictions for

photoassociation rates, 70–73 Radio spectra, comets, 151–153

trap-loss spectrum, 85, 87–88 Recoil techniques

two states by diagonalization, 62 atomic deflection, 173–177

ultracold Cs experiment, 79–80 cold target recoil ion momentum

uniform semiclassical (USC) spectroscopy (COLTRIMS), 165

wavefunction, 69–70 comparison to magnetic angle changing

vibrational motion in long- and results, 181–182

short-range regions, 64–66 limitations, 200

vibrational spacing as function of providing new information about

detuning, 68 electron-impact excitation, 199–200

Photoassociation laser, Orsay experiment, schematic of apparatus at

83–84 Manchester, 174

Planets. See Giant planets and comets two-step laser process eliminating

Population differences, four-wave difficulties, 200–201

mixing, 31 Recycling active atoms, level scheme of

Population exchange, studying dynamics, laser, 244

33–34 Reflection principle, calculating

Franck–Condon factors, 73–75

Q Relaxation oscillation

amplitude spectrum of intensity

Quantum noise of small lasers noise, 224

cavity QED and β, 219–221 damped harmonic oscillator, 223

258 INDEX

intensity-noise strength at low frequency heavenly bodies, 130

versus number of photons in laser laboratory studies in visible region,

cavity, 225 130–131

laser, 222–227 molecular abundances from

neglecting inversion noise for low observations, 135–138

frequencies, 225 Spinor operators, four-wave mixing, 31

photonic damping and atomic Spontaneous emission factor β

damping, 223–224 assumptions of general form, 217–219

spectra of spontaneous emission and calculation, 214–216

cavity resonance, 216 cavity mode in bad-cavity regime,

spectrum of AlGaAs semiconductor 216–217

laser, 226 cavity mode in good-cavity regime, 216

Resonance condition, photoassociation, 58 cavity QED and β, 219–221

R-matrix method, vibrational magnitude, 221–222

wavefunctions, 107 nature of fluctuation threshold

Rotational temperatures, cold molecules, depending on, 230–232

96–99 schematic of couplings between atomic

Rydberg atoms excitation, discrete cavity mode, and

alternative detection method, 189–190 optical continuum, 215

stepwise techniques to study highly spectra, 216

excited, 189 typical geometry for calculating, 215

See also Stepwise laser probing Stark decelerator, cooling technique, 56

Stepwise laser probing

absence of ions when laser is

S off-resonance, 193–194

advantage of UV laser radiation, 191

Saturn allowing molecular rotational levels, 200

far-infrared spectra, 137–138 alternative detection method, 189–190

H2–H2 dimer features in near-infrared deflected metastable targets, 187–199

spectra, 139 efficiency of laser excitation of Rydberg

Infrared Space Observatory (ISO), state, 193

132–133 electronic hardware to control

See also Giant planets interactions, 191

Scaling laws, interpretation and fitting experimental techniques, 190–192

experiments, 70 experiments using coincidence

Scattering length, concept, 3 technique, 198

Schrödinger field operator field ionization and metastable signals in

mode expansion, 12 upper detector, 199

N-particle wave function, 10 field ionization spectrum from H2,

Second-order equal-time intensity 196, 197

correlation function, definition, 42 high Rydberg spectrum, typical using

Self-consistent mean-field approximation, lower detector, 192–193

finite temperatures, 20–23 laser system producing tunable pulsed

Small lasers. See Quantum noise radiation, 190

of small lasers principles, 187–190

Spectroscopy results, 192–199

comets, 145–155 results from upper detector, 197–199

databases and improvements needed, Rydberg series in argon using lower

155–156 detector, 194, 195

INDEX 259

excitation, 188 Ultracold molecules

studying highly excited Rydberg accurate electronic dipole transition

atoms, 189 moments, 108–109

test of Percival–Seaton hypothesis, accurate molecular potential curves,

188–189 108–109

Stimulated Raman photoassociation analytical treatment, 108

relevant energy levels, 97 applications, 54

resonance, 98 atomic lifetime, 87–88

ultracold molecules, 97–98 cesium photoassociation experiment,

Supersonic expansion 79–80

gas, 175 cold atomic source, 80–83

velocity distribution of gas, 175 comparing experiment and theory,

s-wave scattering 109–115

approximation, 7 Cs+2 ion signal, 86

elastic, 3–5 Cs+2 ion signal vs. detuning

expanding wave function in terms of photoassociation laser, 90

partial waves, 5–6 Cs2 1u pure long-range state, 89, 91

expansion in terms of spherical Cs2 0−g pure long-range state, 88–89

harmonics, 6–7 demonstrating use of photoassociation,

ultracold particles, 6 99–100

detection, 84, 85

detection scheme in Orsay

T experiment, 85

determining vibrational wavefunctions,

Temperatures 101–108

rotational and vibrational, 96–99 experimental setup in Orsay experiment,

translational, 93–94 80–84

Thomas–Fermi approximation, formation by photoassociation,

large-condensates, 19 56–57, 100

Time-of-flight formation rate, 111–114

measurements of atomic deflection, Gordon method, 107

176–177 ion spectrum, 88–91

spectra from helium, 178 LeRoy–Bernstein law, 87

temperature measurement, 94 magnetooptical trap device (MOT), 80

Titan, spectroscopy, 143, 144 mapped Fourier method, 101–107

Translational temperature maximum of detected ions, 98

cesium, 93–94 mechanism for formation, 93

temperature measurement through mechanism of formation, 91–92

ballistic expansion, 95 new schemes for making, 116–117

temperature measurement through time Numerov approach, 107

of flight, 94 photoassociation laser, 83–84

Trap-loss spectrum, photoassociation of photoassociation rate, 94–96

cesium, 85, 87–88 photoassociation rates, 109–111

Trapping atoms, applications, 54 photoassociation spectra, 84–91

Triplet state, making molecule, relevant energy levels of stimulated

78–80 Raman photoassociation transition, 97

Tunneling effect, ultracold molecules, R-matrix method, 107

114–115, 116 rotational and vibrational temperatures,

Two-body collisions, Hamiltonian, 14 96–99

260 INDEX

scheme of experimental setup, 81

stimulated Raman photoassociation, Vibrational temperatures, cold molecules,

97, 98 96–99

temperature measurement through Vibrational wavefunctions

ballistic expansion, 95 analytical treatment, 108

temperature measurement through time determination for photoassociated

of flight, 94 molecules, 101–108

theoretical methods, 100–109 Gordon method, 107

time evolution of Cs+ mapped Fourier method, 101–107

2 ion signal, 92

total number of cold atoms in trap, 82 Numerov approach, 107

translational temperature, 93–94 R-matrix method, 107

trap-loss spectrum, 85, 87–88 Visible spectra

tunneling effect, 114–115, 116 comets, 146–149

vapor-loaded MOT, 81–82 giant planets, 132

vibrational wavefunction in outer well Voyager. See Infrared Interferometer

of 0− Spectrometer and Radiometer (IRIS)

g potential for Cs2, 93

zoom of Cs+ 2 ion signal vs. detuning

photoassociation laser, 90 Z

See also Cold molecules;

Photoassociation Zero-energy scattering wavefunction,

Ultraviolet spectra nodal structure, 75–77

comets, 146–149 Zero temperature

giant planets, 132 reflection principle, 73–75

Uranus. See Giant planets mean-field theory, 15–20

Contents of Volumes in This Serial

Volume 1 Volume 3

Properties of Conjugated Molecules, Cross Sections, A. L. Stewart

G. G. Hall and A. T. Amos Radiofrequency Spectroscopy of Stored Ions

Electron Affinities of Atoms and Molecules, I: Storage, H. G. Dehmelt

B. L. Moiseiwitsch Optical Pumping Methods in Atomic

Atomic Rearrangement Collisions, Spectroscopy, B. Budick

B. H. Bransden Energy Transfer in Organic Molecular

The Production of Rotational and Vibrational Crystals: A Survey of Experiments,

Transitions in Encounters between H. C. Wolf

Molecules, K. Takayanagi Atomic and Molecular Scattering from Solid

The Study of Intermolecular Potentials with Surfaces, Robert E. Stickney

Molecular Beams at Thermal Energies, Quantum, Mechanics in Gas Crystal-Surface

H. Pauly and J. P. Toennies van der Waals Scattering, E. Chanoch

Beder

High-Intensity and High-Energy Molecular

Beams, J. B. Anderson, R. P. Andres, and Reactive Collisions between Gas and Surface

J. B. Fen Atoms, Henry Wise and Bernard J. Wood

Volume 4

Volume 2

H. S. W. Massey—A Sixtieth Birthday

The Calculation of van der Waals Tribute, E. H. S. Burhop

Interactions, A. Dalgarno and

W. D. Davison Electronic Eigenenergies of the Hydrogen

Molecular Ion, D. R. Bates and

Thermal Diffusion in Gases, E. A. Mason, R. H. G. Reid

R. J. Munn, and Francis J. Smith

Applications of Quantum Theory to the

Spectroscopy in the Vacuum Ultraviolet, Viscosity of Dilute Gases,

W. R. S. Garton R. A. Buckingham and E. Gal

The Measurement of the Photoionization Positrons and Positronium in Gases,

Cross Sections of the Atomic Gases, P. A. Fraser

James A. R. Samson Classical Theory of Atomic Scattering,

The Theory of Electron–Atom Collisions, A. Burgess and I. C. Percival

R. Peterkop and V. Veldre Born Expansions, A. R. Holt and

Experimental Studies of Excitation in B. L. Moiselwitsch

Collisions between Atomic and Ionic Resonances in Electron Scattering by Atoms

Systems, F. J. de Heer and Molecules, P. G. Burke

Mass Spectrometry of Free Radicals, Relativistic Inner Shell Ionizations,

S. N. Foner C. B. O. Mohr

261

262 CONTENTS OF VOLUMES IN THIS SERIAL

J. B. Hasted E. A. Mason and T. R. Marrero

Measurements of Electron Excitation Theory and Application of Sturmian

Functions, D. W. O. Heddle and Functions, Manuel Rotenberg

R. G. W. Keesing Use of Classical mechanics in the Treatment

Some New Experimental Methods in of Collisions between Massive Systems,

Collision Physics, R. F. Stebbings D. R. Bates and A. E. Kingston

Atomic Collision Processes in Gaseous

Nebulae, M. J. Seaton

Volume 7

Collisions in the Ionosphere, A. Dalgarno

The Direct Study of Ionization in Space, Physics of the Hydrogen Master, C. Audoin,

R. L. F. Boyd J. P. Schermann, and P. Grivet

Molecular Wave Functions: Calculations and

Use in Atomic and Molecular Processes,

Volume 5 J. C. Browne

Localized Molecular Orbitals, Harel

Flowing Afterglow Measurements of

Weinstein, Ruben Pauncz, and

Ion-Neutral Reactions, E. E. Ferguson,

Maurice Cohen

F. C. Fehsenfeld, and A. L. Schmeltekopf

General Theory of Spin-Coupled Wave

Experiments with Merging Beams,

Functions for Atoms and Molecules,

Roy H. Neynaber

J. Gerratt

Radiofrequency Spectroscopy of Stored Ions

Diabatic States of Molecules—Quasi-

II: Spectroscopy, H. G. Dehmelt

Stationary Electronic States, Thomas

The Spectra of Molecular Solids, O. Schnepp F. O’Malley

The Meaning of Collision Broadening of Selection Rules within Atomic Shells,

Spectral Lines: The Classical Oscillator B. R. Judd

Analog, A. Ben-Reuven

Green’s Function Technique in Atomic and

The Calculation of Atomic Transition Molecular Physics, Gy. Csanak,

Probabilities, R. J. S. Crossley H. S. Taylor, and Robert Yaris

Tables of One- and Two-Particle Coefficients A Review of Pseudo-Potentials with

of Fractional Parentage for Configurations Emphasis on Their Application to Liquid

s λ s ′u pq , C. D. H. Chisholm, A. Dalgarno, Metals, Nathan Wiser and A. J. Greenfield

and F. R. Innes

Relativistic Z-Dependent Corrections to

Atomic Energy Levels, Holly Thomis Doyle Volume 8

Volume 6 Destruction, D. McNally

Monte Carlo Trajectory Calculations of

Dissociative Recombination, J. N. Bardsley Atomic and Molecular Excitation in

and M. A. Biondi Thermal Systems, James C. Keck

Analysis of the Velocity Field in Plasmas Nonrelativistic Off-Shell Two-Body Coulomb

from the Doppler Broadening of Spectral Amplitudes, Joseph C. Y. Chen and

Emission Lines, A. S. Kaufman Augustine C. Chen

The Rotational Excitation of Molecules by Photoionization with Molecular Beams,

Slow Electrons, Kazuo Takayanagi and R. B. Cairns, Halstead Harrison, and

Yukikazu Itikawa R. I. Schoen

CONTENTS OF VOLUMES IN THIS SERIAL 263

W. N. Asaad Scattering: An Information-Theoretic

Approach, R. B. Bernstein and R. D. Levine

Inner Shell Ionization by Incident Nuclei,

Volume 9 Johannes M. Hansteen

Stark Broadening, Hans R. Griem

Correlation in Excited States of Atoms,

A. W. Weiss Chemiluminescence in Gases, M. F. Golde

and B. A. Thrush

The Calculation of Electron–Atom Excitation

Cross Sections, M. R. H. Rudge

Collision-Induced Transitions between

Rotational Levels, Takeshi Oka Volume 12

The Differential Cross Section of

Low-Energy Electron–Atom Collisions, Nonadiabatic Transitions between Ionic and

D. Andrick Covalent States, R. K. Janev

Molecular Beam Electric Resonance Recent Progress in the Theory of Atomic

Spectroscopy, Jens C. Zorn and Thomas Isotope Shift, J. Bauche and

C. English R.-J. Champeau

Atomic and Molecular Processes in the Topics on Multiphoton Processes in Atoms,

Martian Atmosphere, Michael B. McElroy P. Lambropoulos

Optical Pumping of Molecules, M. Broyer,

G. Goudedard, J. C. Lehmann, and J. Vigué

Volume 10 Highly Ionized Ions, Ivan A. Sellin

Time-of-Flight Scattering Spectroscopy,

Relativistic Effects in the Many-Electron

Wilhelm Raith

Atom, Lloyd Armstrong, Jr. and Serge

Feneuille Ion Chemistry in the D Region, George

C. Reid

The First Born Approximation, K. L. Bell and

A. E. Kingston

Photoelectron Spectroscopy, W. C. Price

Dye Lasers in Atomic Spectroscopy, Volume 13

W. Lange, J. Luther, and A. Steudel

Atomic and Molecular Polarizabilities—A

Recent Progress in the Classification of the

Review of Recent Advances, Thomas

Spectra of Highly Ionized Atoms,

M. Miller and Benjamin Bederson

B. C. Fawcett

Study of Collisions by Laser Spectroscopy,

A Review of Jovian Ionospheric Chemistry,

Paul R. Berman

Wesley T. Huntress, Jr.

Collision Experiments with Laser-Excited

Atoms in Crossed Beams, I. V. Hertel and

Volume 11 W. Stoll

Scattering Studies of Rotational and

The Theory of Collisions between Charged Vibrational Excitation of Molecules,

Particles and Highly Excited Atoms, Manfred Faubel and J. Peter Toennies

I. C. Percival and D. Richards Low-Energy Electron Scattering by Complex

Electron Impact Excitation of Positive Ions, Atoms: Theory and Calculations,

M. J. Seaton R. K. Nesbet

The R-Matrix Theory of Atomic Process, Microwave Transitions of Interstellar Atoms

P. G. Burke and W. D. Robb and Molecules, W. B. Somerville

264 CONTENTS OF VOLUMES IN THIS SERIAL

Excitation of Atoms by Electron Impact,

Resonances in Electron Atom and Molecule D. W. O. Heddle

Scattering, D. E. Golden Coherence and Correlation in Atomic

The Accurate Calculation of Atomic Collisions, H. Kleinpoppen

Properties by Numerical Methods, Brian Theory of Low Energy Electron-Molecule

C. Webster, Michael J. Jamieson, and Collisions, P. G. Burke

Ronald F. Stewart

(e, 2e) Collisions, Erich Weigold and Ian

E. McCarthy Volume 16

Forbidden Transitions in One- and

Two-Electron Atoms, Richard Marrus and Atomic Hartree–Fock Theory, M. Cohen and

Peter J. Mohr R. P. McEachran

Semiclassical Effects in Heavy-Particle Experiments and Model Calculations to

Collisions, M. S. Child Determine Interatomic Potentials, R. Düren

Atomic Physics Tests of the Basic Concepts Sources of Polarized Electrons, R. J. Celotta

in Quantum Mechanics, Francis M. Pipkin and D. T. Pierce

Quasi-Molecular Interference Effects in Theory of Atomic Processes in Strong

Ion–Atom Collisions, S. V. Bobashev Resonant Electromagnetic Fields, S. Swain

Rydberg Atoms, S. A. Edelstein and Spectroscopy of Laser-Produced Plasmas,

T. F. Gallagher M. H. Key and R. J. Hutcheon

UV and X-Ray Spectroscopy in Astrophysics, Relativistic Effects in Atomic Collisions

A. K. Dupree Theory, B. L. Moiseiwitsch

Parity Nonconservation in Atoms: Status of

Theory and Experiment, E. N. Fortson and

Volume 15

L. Wilets

Negative Ions, H. S. W. Massey

Atomic Physics from Atmospheric and Volume 17

Astrophysical Studies, A. Dalgarno

Collisions of Highly Excited Atoms, Collective Effects in Photoionization of

R. F. Stebbings Atoms, M. Ya. Amusia

Theoretical Aspects of Positron Collisions in Nonadiabatic Charge Transfer,

Gases, J. W. Humberston D. S. F. Crothers

Experimental Aspects of Positron Collisions Atomic Rydberg States, Serge Feneuille and

in Gases, T. C. Griffith Pierre Jacquinot

Reactive Scattering: Recent Advances in Superfluorescence, M. F. H. Schuurmans,

Theory and Experiment, Richard Q. H. F. Vrehen, D. Polder, and

B. Bernstein H. M. Gibbs

Ion–Atom Charge Transfer Collisions at Low Applications of Resonance Ionization

Energies, J. B. Hasted Spectroscopy in Atomic and Molecular

Aspects of Recombination, D. R. Bates Physics, M. G. Payne, C. H. Chen,

The Theory of Fast Heavy Particle Collisions, G. S. Hurst, and G. W. Foltz

B. H. Bransden Inner-Shell Vacancy Production in Ion–Atom

Atomic Collision Processes in Controlled Collisions, C. D. Lin and Patrick Richard

Thermonuclear Fusion Research, Atomic Processes in the Sun, P. L. Dufton and

H. B. Gilbody A. E. Kingston

CONTENTS OF VOLUMES IN THIS SERIAL 265

Photoelectrons, N. A. Cherepkov

Theory of Electron–Atom Scattering in a

Radiation Field, Leonard Rosenberg

Positron–Gas Scattering Experiments, Talbert Volume 20

S. Stein and Walter E. Kauppila

Ion–Ion Recombination in an Ambient Gas,

Nonresonant Multiphoton Ionization of D. R. Bates

Atoms, J. Morellec, D. Normand, and

G. Petite Atomic Charges within Molecules, G. G. Hall

Classical and Semiclassical Methods in Experimental Studies on Cluster Ions,

Inelastic Heavy-Particle Collisions, T. D. Mark and A. W. Castleman, Jr.

A. S. Dickinson and D. Richards Nuclear Reaction Effects on Atomic

Recent Computational Developments in the Inner-Shell Ionization, W. E. Meyerhof and

Use of Complex Scaling in Resonance J.-F. Chemin

Phenomena, B. R. Junker Numerical Calculations on Electron-Impact

Direct Excitation in Atomic Collisions: Ionization, Christopher Bottcher

Studies of Quasi-One-Electron Systems, Electron and Ion Mobilities, Gordon

N. Anderson and S. E. Nielsen R. Freeman and David A. Armstrong

Model Potentials in Atomic Structure, On the Problem of Extreme UV and X-Ray

A. Hibbert Lasers, I. I. Sobel’man and

Recent Developments in the Theory of A. V. Vinogradov

Electron Scattering by Highly Polar Radiative Properties of Rydberg States in

Molecules, D. W. Norcross and Resonant Cavities, S. Haroche and

L. A. Collins J. M. Ralmond

Quantum Electrodynamic Effects in Few- Rydberg Atoms: High-Resolution

Electron Atomic Systems, G. W. F. Drake Spectroscopy and Radiation Interaction—

Rydberg Molecules, J. A. C. Gallas,

G. Leuchs, H. Walther, and H. Figger

Volume 19

Atoms with Fully Stripped Ions,

B. H. Bransden and R. K. Janev Subnatural Linewidths in Atomic

Interactions of Simple Ion–Atom Systems, Spectroscopy, Dennis P. O’Brien, Pierre

J. T. Park Meystre, and Herbert Walther

High-Resolution Spectroscopy of Stored Molecular Applications of Quantum

Ions, D. J. Wineland, Wayne M. Itano, and Defect Theory, Chris H. Greene and

R. S. Van Dyck, Jr. Ch. Jungen

Spin-Dependent Phenomena in Inelastic Theory of Dielectronic Recombination,

Electron–Atom Collisions, K. Blum and Yukap Hahn

H. Kleinpoppen Recent Developments in Semiclassical

The Reduced Potential Curve Method for Floquet Theories for Intense-Field

Diatomic Molecules and Its Applications, Multiphoton Processes, Shih-I Chu

F. Jenč Scattering in Strong Magnetic Fields,

The Vibrational Excitation of Molecules by M. R. C. McDowell and M. Zarcone

Electron Impact, D. G. Thompson Pressure Ionization, Resonances, and the

Vibrational and Rotational Excitation in Continuity of Bound and Free States,

Molecular Collisions, Manfred Faubel R. M. More

266 CONTENTS OF VOLUMES IN THIS SERIAL

Ionization of Atoms, S. J. Smith and

Positronium—Its Formation and Interaction G. Leuchs

with Simple Systems, J. W. Humberston Optical Pumping and Spin Exchange in Gas

Experimental Aspects of Positron and Cells, R. J. Knize, Z. Wu, and W. Happer

Positronium Physics, T. C. Griffith Correlations in Electron–Atom Scattering,

Doubly Excited States, Including New A. Crowe

Classification Schemes, C. D. Lin

Measurements of Charge Transfer and Volume 25

Ionization in Collisions Involving

Hydrogen Atoms, H. B. Gilbody Alexander Dalgarno: Life and Personality,

Electron–Ion and Ion–Ion Collisions with David R. Bates and George A. Victor

Intersecting Beams, K. Dolder and B. Pearl Alexander Dalgarno: Contributions to

Electron Capture by Simple Ions, Edward Atomic and Molecular Physics, Neal Lane

Pollack and Yukap Hahn Alexander Dalgarno: Contributions to

Relativistic Heavy-Ion–Atom Collisions, Aeronomy, Michael B. McElroy

R. Anholt and Harvey Gould Alexander Dalgarno: Contributions to

Continued-Fraction Methods in Atomic Astrophysics, David A. Williams

Physics, S. Swain Dipole Polarizability Measurements, Thomas

M. Miller and Benjamin Bederson

Flow Tube Studies of Ion–Molecule

Volume 23 Reactions, Eldon Ferguson

Differential Scattering in He He and

Vacuum Ultraviolet Laser Spectroscopy of He+ He Collisions at KeV Energies,

Small Molecules, C. R. Vidal R. F. Stebbings

Foundations of the Relativistic Theory of Atomic Excitation in Dense Plasmas,

Atomic and Molecular Structure, Jon C. Weisheit

Ian P. Grant and Harry M. Quiney

Pressure Broadening and Laser-Induced

Point-Charge Models for Molecules Derived Spectral Line Shapes, Kenneth M. Sando

from Least-Squares Fitting of the Electric and Shih-I Chu

Potential, D. E. Williams and Ji-Min Yan

Model-Potential Methods, G. Laughlin and

Transition Arrays in the Spectra of Ionized G. A. Victor

Atoms, J. Bauche, C. Bauche-Arnoult, and

M. Klapisch Z-Expansion Methods, M. Cohen

Photoionization and Collisional Ionization of Schwinger Variational Methods, Deborah

Excited Atoms Using Synchroton and Kay Watson

Laser Radiation, F. J. Wuilleumier, Fine-Structure Transitions in Proton-Ion

D. L. Ederer, and J. L. Picqué Collisions, R. H. G. Reid

Electron Impact Excitation, R. J. W. Henry

and A. E. Kingston

Volume 24 Recent Advances in the Numerical

Calculation of Ionization Amplitudes,

The Selected Ion Flow Tube (SIDT): Studies Christopher Bottcher

of Ion–Neutral Reactions, D. Smith and The Numerical Solution of the Equations of

N. G. Adams Molecular Scattering, A. C. Allison

Near-Threshold Electron–Molecule High Energy Charge Transfer, B. H. Bransden

Scattering, Michael A. Morrison and D. P. Dewangan

CONTENTS OF VOLUMES IN THIS SERIAL 267

W. R. Johnson and E. Weigold

Relativistic Sturmian and Finite Basis Set Role of Autoionizing States in Multiphoton

Methods in Atomic Physics, G. W. F. Drake Ionization of Complex Atoms, V. I. Lengyel

and S. P. Goldman and M. I. Haysak

Dissociation Dynamics of Polyatomic Multiphoton Ionization of Atomic Hydrogen

Molecules, T. Uzer Using Perturbation Theory, E. Karule

Photodissociation Processes in Diatomic

Molecules of Astrophysical Interest,

Kate P. Kirby and Ewine F. van Dishoeck Volume 28

The Abundances and Excitation of

Interstellar Molecules, John H. Black The Theory of Fast Ion–Atom Collisions,

J. S. Briggs and J. H. Macek

Some Recent Developments in the

Volume 26 Fundamental Theory of Light,

Peter W. Milonni and Surendra Singh

Comparisons of Positrons and Electron Squeezed States of the Radiation Field,

Scattering by Gases, Walter E. Kauppila Khalid Zaheer and M. Suhail Zubairy

and Talbert S. Stein Cavity Quantum Electrodynamics,

Electron Capture at Relativistic Energies, E. A. Hinds

B. L. Moiseiwitsch

The Low-Energy, Heavy Particle

Collisions—A Close-Coupling Treatment, Volume 29

Mineo Kimura and Neal F. Lane

Vibronic Phenomena in Collisions of Atomic Studies of Electron Excitation of Rare-Gas

and Molecular Species, V. Sidis Atoms into and out of Metastable Levels

Associative Ionization: Experiments, Using Optical and Laser Techniques,

Potentials, and Dynamics, John Weiner, Chun C. Lin and L. W. Anderson

Françoise Masnou-Sweeuws, and Cross Sections for Direct Multiphoton

Annick Giusti-Suzor Ionionization of Atoms, M. V. Ammosov,

On the β Decay of 187 Re: An Interface of N. B. Delone, M. Yu. Ivanov, I. I. Bondar,

Atomic and Nuclear Physics and and A. V. Masalov

Cosmochronology, Zonghau Chen, Collision-Induced Coherences in Optical

Leonard Rosenberg, and Larry Spruch Physics, G. S. Agarwal

Progress in Low Pressure Mercury-Rare Gas Muon-Catalyzed Fusion, Johann Rafelski and

Discharge Research, J. Maya and Helga E. Rafelski

R. Lagushenko Cooperative Effects in Atomic Physics,

J. P. Connerade

Multiple Electron Excitation, Ionization, and

Volume 27 Transfer in High-Velocity Atomic and

Molecular Collisions, J. H. McGuire

Negative Ions: Structure and Spectra,

David R. Bates

Electron Polarization Phenomena in Volume 30

Electron–Atom Collisions,

Joachim Kessler Differential Cross Sections for Excitation of

Electron–Atom Scattering, I. E. McCarthy Helium Atoms and Helium-Like Ions by

and E. Weigold Electron Impact, Shinobu Nakazaki

268 CONTENTS OF VOLUMES IN THIS SERIAL

Impact on Excited Atomic Species, Processes, M. R. Flannery

S. Trajmar and J. C. Nickel Studies of State-Selective Electron Capture in

The Dissociative Ionization of Simple, Atomic Hydrogen by Translational Energy

Molecules by Fast Ions, Colin J. Latimer Spectroscopy, H. B. Gilbody

Theory of Collisions between Laser Cooled Relativistic Electronic Structure of Atoms

Atoms, P. S. Julienne, A. M. Smith, and and Molecules, I. P. Grant

K. Burnett The Chemistry of Stellar Environments,

Light-Induced Drift, E. R. Eliel D. A. Howe, J. M. C. Rawlings, and

Continuum Distorted Wave Methods in D. A. Williams

Ion-Atom Collisions, Derrick Positron and Positronium Scattering at Low

S. F. Crothers and Louis J. Dubé Energies, J. W. Humberston

How Perfect are Complete Atomic Collision

Experiments?, H. Kleinpoppen and

Volume 31 H. Handy

Adiabatic Expansions and Nonadiabatic

Energies and Asymptotic Analysis Effects, R. McCarroll and D. S. F. Crothers

for Helium Rydberg States, Electron Capture to the Continuum,

G. W. F. Drake B. L. Moiseiwitsch

Spectroscopy of Trapped Ions, How Opaque Is a Star? M. J. Seaton

R. C. Thompson

Studies of Electron Attachment at

Phase Transitions of Stored Laser-Cooled Thermal Energies Using the Flowing

Ions, H. Walther Afterglow–Langmuir Technique,

Selection of Electronic States in Atomic David Smith and Patrik Španěl

Beams with Lasers, Jacques Baudon, Exact and Approximate Rate Equations in

Rudolf Düren, and Jacques Robert Atom-Field Interactions, S. Swain

Atomic Physics and Non-Maxwellian Atoms in Cavities and Traps, H. Walther

Plasmas, Michèle Lamoureux

Some Recent Advances in Electron-Impact

Excitation of n = 3 States of Atomic

Hydrogen and Helium, J. F. Williams and

Volume 32 J. B. Wang

Atomic Nitrogen, K. L. Bell and

A. E. Kingston Volume 33

Positronium Formation by Positron Impact on Principles and Methods for Measurement of

Atoms at Intermediate Energies, Electron Impact Excitation Cross Sections

B. H. Bransden and C. J. Noble for Atoms and Molecules by Optical

Electron–Atom Scattering Theory and Techniques, A. R. Filippelli, Chun C. Lin,

Calculations, P. G. Burke L. W. Andersen, and J. W. McConkey

Terrestrial and Extraterrestrial H+

3 , Alexander Benchmark Measurements of Cross Sections

Dalgarno for Electron Collisions: Analysis of

Indirect Ionization of Positive Atomic Ions, Scattered Electrons, S. Trajmar and

K. Dolder J. W. McConkey

Quantum Defect Theory and Analysis of Benchmark Measurements of Cross Sections

High-Precision Helium Term Energies, for Electron Collisions: Electron Swarm

G. W. F. Drake Methods, R. W. Crompton

CONTENTS OF VOLUMES IN THIS SERIAL 269

Sections for Collisions of Simple Heavy Ionization of Positive Ions, D. L. Moores

Particles, H. B. Gilbody and K. J. Reed

The Role of Theory in the Evaluation and Dissociative Recombination: Crossing and

Interpretation of Cross-Section Data, Tunneling Modes, David R. Bates

Barry I. Schneider

Analytic Representation of Cross-Section

Data, Mitio Inokuti, Mineo Kimura, Volume 35

M. A. Dillon, Isao Shimamura

Electron Collisions with N2 , O2 and O: What Laser Manipulation of Atoms, K. Sengstock

We Do and Do Not Know, Yukikazu and W. Ertmer

Itikawa Advances in Ultracold Collisions:

Need for Cross Sections in Fusion Plasma Experiment and Theory, J. Weiner

Research, Hugh P. Summers Ionization Dynamics in Strong Laser Fields,

Need for Cross Sections in Plasma Chemistry, L. F. DiMauro and P. Agostini

M. Capitelli, R. Celiberto, and Infrared Spectroscopy of Size Selected

M. Cacciatore Molecular Clusters, U. Buck

Guide for Users of Data Resources, Jean Femtosecond Spectroscopy of Molecules and

W. Gallagher Clusters, T. Baumer and G. Gerber

Guide to Bibliographies, Books, Reviews, Calculation of Electron Scattering on

and Compendia of Data on Atomic Hydrogenic Targets, I. Bray and

Collisions, E. W. McDaniel and A. T. Stelbovics

E. J. Mansky Relativistic Calculations of Transition

Amplitudes in the Helium Isoelectronic

Sequence, W. R. Johnson, D. R. Plante, and

Volume 34 J. Sapirstein

Rotational Energy Transfer in Small

Atom Interferometry, C. S. Adams, O. Carnal, Polyatomic Molecules, H. O. Everitt and

and J. Mlynek F. C. De Lucia

Optical Tests of Quantum Mechanics, R. Y.

Chiao, P. G. Kwiat, and A. M. Steinberg

Classical and Quantum Chaos in Atomic Volume 36

Systems, Dominique Delande and

Andreas Buchleitner Complete Experiments in Electron–Atom

Measurements of Collisions between Collisions, Nils Overgaard Andersen, and

Laser-Cooled Atoms, Thad Walker and Klaus Bartschat

Paul Feng Stimulated Rayleigh Resonances and

The Measurement and Analysis of Electric Recoil-Induced Effects, J.-Y. Courtois and

Fields in Glow Discharge Plasmas, G. Grynberg

J. E. Lawler and D. A. Doughty Precision Laser Spectroscopy Using

Polarization and Orientation Phenomena in Acousto-Optic Modulators, W. A. van

Photoionization of Molecules, Wijngaarden

N. A. Cherepkov Highly Parallel Computational Techniques for

Role of Two-Center Electron–Electron Electron–Molecule Collisions,

Interaction in Projectile Electron Carl Winstead and Vincent McKoy

Excitation and Loss, E. C. Montenegro, Quantum Field Theory of Atoms and

W. E. Meyerhof, and J. H. McGuire Photons, Maciej Lewenstein and Li You

270 CONTENTS OF VOLUMES IN THIS SERIAL

Volume 37 Volume 40

Resonators, Waveguides, and Traps, D. Commins

Jonathan P. Dowling and Julio High-Precision Calculations for the Ground

Gea-Banacloche and Excited States of the Lithium Atom,

Optical Lattices, P. S. Jessen and Frederick W. King

I. H. Deutsch Storage Ring Laser Spectroscopy, Thomas

Channeling Heavy Ions through Crystalline U. Kühl

Lattices, Herbert F. Krause and Sheldon Laser Cooling of Solids, Carl E. Mungan and

Datz Timothy R. Gosnell

Evaporative Cooling of Trapped Atoms, Optical Pattern Formation, L. A. Lugiato,

Wolfgang Ketterle and N. J. van Druten M. Brambilla, and A. Gatti

Nonclassical States of Motion in Ion Traps,

J. I. Cirac, A. S. Parkins, R. Blatt, and

P. Zoller Volume 41

The Physics of Highly-Charged Heavy Ions

Revealed by Storage/Cooler Rings, Two-Photon Entanglement and Quantum

P. H. Mokler and Th. Stöhlker Reality, Yanhua Shih

Quantum Chaos with Cold Atoms,

Mark G. Raizen

Volume 38 Study of the Spatial and Temporal Coherence

of High-Order Harmonics, Pascal Salières,

Electronic Wavepackets, Robert R. Jones and Ann L’Huiller Philippe Antoine, and

L. D. Noordam Maciej Lewenstein

Chiral Effects in Electron Scattering by Atom Optics in Quantized Light Fields,

Molecules, K. Blum and D. G. Thompson Matthias Freyburger, Alois M. Herkommer,

Optical and Magneto-Optical Spectroscopy of Daniel S. Krähmer, Erwin Mayr, and

Point Defects in Condensed Helium, Wolfgang P. Schleich

Serguei I. Kanorsky and Antoine Weis Atom Waveguides, Victor I. Balykin

Rydberg Ionization: From Field to Photon, Atomic Matter Wave Amplification by

G. M. Lankhuijzen and L. D. Noordam Optical Pumping, Ulf Janicke and

Studies of Negative Ions in Storage Rings, Martin Wilkens

L. H. Andersen, T. Andersen, and

P. Hvelplund

Single-Molecule Spectroscopy and Quantum Volume 42

Optics in Solids, W. E. Moerner,

R. M. Dickson, and D. J. Norris Fundamental Tests of Quantum Mechanics,

Edward S. Fry and Thomas Walther

Wave-Particle Duality in an Atom

Volume 39 Interferometer, Stephan Dürr and

Gerhard Rempe

Author and Subject Cumulative Index Atom Holography, Fujio Shimizu

Volumes 1–38 Optical Dipole Traps for Neutral Atoms,

Author Index Rudolf Grimm, Matthias Weidemüller, and

Subject Index Yurii B. Ovchinnikov

Appendix: Tables of Contents of Volumes Formation of Cold (T 1K) Molecules,

1–38 and Supplements J. T. Bahns, P. L. Gould, and W. C. Stwalley

CONTENTS OF VOLUMES IN THIS SERIAL 271

C. J. Joachain, M. Dorr, and N. J. Kylstra Interactions, Rainer Hippler

Coherent Control of Atomic, Molecular, and Recent Applications of Gaseous Discharges:

Electronic Processes, Moshe Shapiro and Dusty Plasmas and Upward-Directed

Paul Brumer Lightning, Ara Chutjian

Resonant Nonlinear Optics in Phase Coherent Opportunities and Challenges for Atomic,

Media, M. D. Lukin, P. Hemmer, and Molecular, and Optical Physics in Plasma

M. O. Scully Chemistry, Kurl Becker, Hans Deutsch, and

The Characterization of Liquid and Solid Mitio Inokuti

Surfaces with Metastable Helium Atoms,

H. Morgner

Quantum Communication with Entangled Volume 44

Photons, Harald Weinfurter

Mechanisms of Electron Transport in

Electrical Discharges and Electron

Collision Cross Sections, Hiroshi Tanaka

Volume 43 and Osamu Sueoka

Theoretical Consideration of Plasma-

Plasma Processing of Materials and Atomic, Processing Processes, Mineo Kimura

Molecular, and Optical Physics: An Electron Collision Data for Plasma-

Introduction, Hiroshi Tanaka and Processing Gases, Loucas

Mitio Inokuti G. Christophorou and James K. Olthoff

The Boltzmann Equation and Transport Radical Measurements in Plasma Processing,

Coefficients of Electrons in Weakly Ionized Toshio Goto

Plasmas, R. Winkler Radio-Frequency Plasma Modeling for

Electron Collision Data for Plasma Chemistry Low-Temperature Processing, Toshiaki

Modeling, W. L. Morgan Makabe

Electron–Molecule Collisions in Electron Interactions with Excited Atoms and

Low-Temperature Plasmas: The role Molecules, Loucas G. Christophorou and

of Theory, Carl Winstead and James K. Olthoff

Vincent McKoy

Electron Impact Ionization of Organic

Silicon Compounds, Ralf Basner, Volume 45

Kurt Becker, Hans Deutsch, and

Martin Schmidt Comparing the Antiproton and Proton, and

Kinetic Energy Dependence of Ion–Molecule Opening the Way to Cold Antihydrogen,

Reactions Related to Plasma Chemistry, G. Gabrielse

P. B. Armentrout Medical Imaging with Laser-Polarized Noble

Physicochemical Aspects of Atomic and Gases, Timothy Chupp and Scott Swanson

Molecular Processes in Reactive Plasmas, Polarization and Coherence Analysis of the

Yoshihiko Hatano Optical Two-Photon Radiation from the

Ion–Molecule Reactions, Werner Lindinger, Metastable 22 S1/2 State of Atomic

Armin Hansel, and Zdenek Herman Hydrogen, Alan J. Duncan, Hans

Uses of High-Sensitivity White-Light Kleinpoppen, and Marlan O. Scully

Absorption Spectroscopy in Chemical Laser Spectroscopy of Small Molecules,

Vapor Deposition and Plasma Processing, W. Demtröder, M. Keil, and H. Wenz

L. W. Anderson, A. N. Goyette, and Coulomb Explosion Imaging of Molecules,

J. E. Lawler Z. Vager

272 CONTENTS OF VOLUMES IN THIS SERIAL

(T ≤ 200 μK) via Photoassociation in a

Femtosecond Quantum Control, T. Brixner, Gas of Laser-Cooled Atoms, Francoise

N. H. Damrauer and G. Gerber Masnou-Seeuws and Pierre Pillet

Coherent Manipulation of Atoms and Molecular Emissions from the Atmospheres

Molecules by Sequential Laser Pulses, of Giant Planets and Comets: Needs for

N. V. Vitanov, M. Fleischhauer, B. W. Shore, Spectroscopic and Collision Data,

and K. Bergmann Yukikazu Itikawa, Sang Joon Kim, Yong Ha

Slow, Ultraslow, Stored, and Frozen Light, Kim, and Y. C. Minh

Andrey B. Matsko, Olga Kocharovskaya, Studies of Electron-Excited Targets Using

Yuri Rostovtsev, George R. Welch, Recoil Momentum Spectroscopy with

Alexander S. Zibrov, and Marlan Laser Probing of the Excited State, Andrew

O. Scully James Murray and Peter Hammond

Longitudinal Interferometry with Atomic Quantum Noise of Small Lasers,

Beams, S. Gupta, D. A. Kokorowski, J. P. Woerdman, N. J. van Druten,

R. A. Rubenstein, and W. W. Smith and M. P. van Exter

Volume 47

P. Meystre

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