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GETTING STARTED ON TIME-RESOLVED MOLECULAR
SPECTROSCOPY
Getting Started on Time-Resolved
Molecular Spectroscopy
Jeffrey A. Cina
University of Oregon
3
3
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For Barbara, of course.
Preface
Well, it has been quite an adventure so far. It was my good fortune to be drawn
into the theory of ultrafast spectroscopy early in the femtosecond era, due in large
part to the prior influence of Rick Heller’s wave-packet descriptions of continuous-
wave spectroscopies (thank you, Laurie!); Bob Silbey’s coaching during the 1980’s,
when multi-pulse optical-phase-controlled picosecond measurements were first under
consideration; and the pleasure and long-term benefit of collaboration with Norbert
Scherer, Stuart Rice, Graham Fleming, and other co-workers at Chicago. At that
stage, one had to find one’s own way, and for me that way started with ordinary
time-dependent perturbation theory as I’d learned it in Bob Harris’s (personally life-
changing) quantum mechanics classes at Berkeley, coupled with a desire to illuminate
the dynamics underlying optical measurements in terms of the evolving nuclear wave
packets that accompany each molecular electronic state.
It hadn’t occurred to me to write this book, or any other, but in 2011 I was in a bit
of a hiatus that came at the end of a multi-year group-reading project with co-workers
at Oregon on L&L’s Electrodynamics of Continuous Media. At Bob Mazo’s suggestion,
Sonke Adlung from Oxford University Press called sometime that year and asked if I
might like to write a book. It happened that I was running a fever at the time and
said, “Sure!”
So, here you have it, the result of the succeeding decade of puzzlement, formulation,
and reformulation—aided by the patience and helpful advice of the numerous collab-
orators and colleagues whose names are among those listed in my Acknowledgements,
hopefully without any inadvertent omissions.
There are valuable treatises already available on the principles of nonlinear optical
spectroscopy of molecular and material systems, notably those by Shaul Mukamel
and Minhaeng Cho.1,2,3,4 The coverage of those works goes beyond what is presented
here. So why write another? I believe that the ultrafast community could benefit
from a deliberately accessible, stepwise treatment (which doesn’t mean an easy one),
more of a textbook than a comprehensive exposition, which can serve as a bridge
between the graduate-level training in quantum mechanics that’s standard in Physical
Chemistry programs and the advanced formulations that serve as guidebooks for those
practicing in the field. The standard approach is to start from the equilibrium density
1 S. Mukamel, Principles of Nonlinear Optical Spectroscopy (Oxford University Press, New York,
1999).
2 M. Cho, Two-Dimensional Optical Spectroscopy (CRC Press, Boca Raton, 2009).
3 D. J. Tannor, Introduction to Quantum Mechanics. A Time-Dependent Perspective (University
Science Books, Sausalito, 2007).
4 J. Yuen-Zhou, J. J. Krich, I. Kassal, A. Johnson, and A. Aspuru-Guzik, Ultrafast Spectroscopy:
Quantum Information and Wavepackets, (IOP Publishing, Bristol, 2014).
viii Preface
matrix of the target molecule and express nonlinear optical signals as a convolution
of the appropriate nonlinear optical response functions with the electric field of the
incident laser pulses. In addition, informed by very early analyses of multi-wave mixing
in nonlinear optical crystals, conventional descriptions are often couched in terms of
optical wave propagation in extended media. Everything in the present text is (or
should be!) physically consistent with the widely applied existing theoretical analyses.
Applications of existing descriptions sometimes tend, in my view, to lose track of
the molecular-level dynamics underlying ultrafast signals, in part because those de-
scriptions compel, or at least encourage one to think about both bra- and ket-sides of
the density operator simultaneously. On the other hand, informed by the superposition
principle, framing things at least initially as a sum of terms in Hilbert space having
various orders in the external-field strengths makes it easier to think about the perti-
nent contributions to the molecular state one at a time. What is developed, analyzed,
and interpreted in terms of Hilbert-space wave functions can easily be converted to a
density-matrix description through a manipulation that takes just a couple of lines.
The wave-propagation picture of nonlinear optical response, while important for
experimental purposes, tends to obscure the fact that, even in an extended sample, each
molecule can often be regarded as undergoing absorption, fluorescence, and Raman
scattering all by itself, as well as acquiring the nonlinear induced dipole moments that
give rise to time-resolved signals. One goal of this text is to formulate as much as
possible in terms of nonlinear induced molecular dipoles—these are ultimately to be
expressed as quantum mechanical overlaps between pairs of multi-pulse wave packets—
and to derive any necessary macroscopic wave-propagation aspects, such as wave-
vector matching, from that microscopic starting point.
The strength of treatments based on nonlinear optical response functions is their
generality. Nonlinear optical signals are to be derived from that fundamental under-
pinning by convolving the relevant response functions with the actual form of the in-
cident laser pulses by multidimensional integration over time variables. It is the case,
though, that such an approach encodes much quantum dynamical information that is
not of immediate use in calculating or interpreting the actual laser-driven dynamics
under consideration. Those strategies sometimes tend, in practice, to invite simplified
comprehensive but phenomenological descriptions that do not attach directly to the
specific, perhaps non-generic form of the regions of the molecular potential energy
surfaces that govern the measured signal.
The treatment put forward here reverses the order of operation between quantum
mechanical averaging and integration over time. It carries out the latter first, with
the use of pulse propagators, operators analogous to those sometimes used in magnetic
resonance spectroscopy, which encapsulate the influence of a nonzero-duration laser
pulse within an instantaneously acting quantum mechanical operator. The reduced
pulse propagators that transfer nuclear wave packets between electronic potential en-
ergy surfaces under the influence of the external fields, reshaping them in the process,
capture the elements of coherent control that are inherent in short-pulse optical spec-
troscopy. This approach puts the focus on the motion of nuclear wave packets in the
optically accessed regions of the electronic potential energy surfaces on which they
evolve. It declines the frequent practice in work-ups based on nonlinear response func-
Preface ix
tions of idealizing the characteristics of the experimentally available light pulses and,
in effect, regarding those response functions themselves as constituting signals, rather
than signal transducers. As mentioned above, the working expressions arrived at here
present signal contributions as overlaps between well characterized individual multi-
pulse nuclear wave packets.
For ease of use and at the cost of some redundancy, I’ve tried to make each chapter
of this book usable and comprehensible on its own. There are some slight inconsisten-
cies of notation between chapters, so unless the reader is advised to do so, applying a
formula from one chapter to an equation in another should be done with caution.
In lieu of end-of-chapter problems, there are many boxed exercises embedded in
the text. By and large, these represent the type of derivation or physical analysis that
I work through to consolidate my own grasp of the ideas at hand. It’s my guess that
readers who excuse themselves from these exercises will be sacrificing something in
the depth of their understanding.
The final portion of most chapters consists of illustrative signal calculations. Car-
rying these out or interpreting their form is both our reward for slogging through the
underlying theory and a pale substitute for the experiential satisfaction of performing
actual measurements. The molecular models that are targeted in these calculations
are chosen to facilitate a thorough interpretation in terms of the underlying molecu-
lar dynamics. It is hoped that these illustrations will help inform what may be the
less complete interpretations that are possible with more complicated experimental
targets.
There is a smattering of references throughout the text but no comprehensive
bibliography. The works cited are just a few of those I found helpful or inspiring.
Many others could undoubtedly have served as well or better; the ones I mention can
perhaps serve as points of entry in the search for other relevant examples.
With help from the many colleagues who have read portions of this text, I’ve tried
hard to root out conceptual misdirection and outright errors. From experience, I know
that there’s no such thing as a small mistake in a scientific text. My sincere apology
for any that may remain.
Personal taste has a significant influence in science (gasp!), and this textbook
reflects my own. I hope, though, that the treatment given here will be to the liking of
at least some readers. I presume further to hope that, after working their way through
this book, those who persevere in doing so will be equipped to make the best use of
more sophisticated methodologies, gaining as much physical insight as possible and
avoiding some of the pitfalls to which applications of those approaches occasionally
give rise.
Jeff Cina
University of Oregon
2021
Acknowledgements
My heartfelt thanks to the following individuals and organizations: y’all know what for.
John Adamovics, Paul Alivisatos, Rise Ando, Ara Apkarian, Sonke Adlung, Natasha
Aristov, Alan Aspuru-Guzik, Bridgette Barry, Mark Berg, Berkeley Chemists for
Peace, Jason Biggs, Sandra Bigtree, Isabella Bischel, Eric Bittner, Harry Bonham,
Stephen Bradforth, Bill Braunlin, Paul Brumer, Irene Burghardt, Carlos Bustamante,
Laurie Butler, Carl Bybee, Jianshu Cao, Roger Carlson, Howard Carmichael, Sister
Carola FSPA, Craig Chapman, Xiaolu Cheng, Minhaeng Cho, Gerri Hoffman Cina,
Merrill T. Cina, Zoë Cina-Sklar, Rob Coalson, Devin Daniels, Joshua Daniels, Julia
Daniels, Rebecca Daniels, Peter Dardi, Brent Davidson, Jahan Dawlaty, Peter Dewey,
Jenni Dobbins, Mike and Carol Drake, Camille and Henry Dreyfus Foundation, Tom
Dyke, Ellen Epstein, my many friends at Espresso Roma, Elaine Finley Giannone,
Graham Fleming, Joan Florsheim, Ignacio Franco, David Frank, Karl Freed, Sarah
Fuchs, Rosemary Garrison, Ibrahim Gassama, Diane Gerth, Michelle Golden, Evi
Goldfield, Eoghan Gormley, John Simon Guggenheim Memorial Foundation, John
Hardwick, Alex Harris, Charles Harris, Christine Harris, Jerry Harris, Katherine Har-
ris, Robert A. Harris (my former PhD advisor, an exemplar of science, and a lifelong
friend), Ray Heath, Rick Heller, Eric Hiller, Maddie Holst, Travis Humble, Katharine
Hunt, Heide Ibrahim, Deb Jackson, Suggy Jang, Truus Jansen, David Jonas, Tara
Jones, Taiha Joo, Chanelle Jumper, Joe Kao, Mike Kellman, Alexis Kiessling, Dmitri
Kilin, Young-Kee Kim, Phil Kovac, Peter Kovach, Cindy Larson, Larry LeSueur, Sis-
ter Leora FSPA, Susan Levine-Friedman, Mark Limont, Katja Lindenberg, Giulia Lip-
parini, Andy Marcus, Alex Matro, Karin Matsumoto, Jack Maurer, Bob Mazo, David
McCamant, Alden Mead, Horia Metiu, Stan Micklavzina, Coleen Miller, Florabelle
Moses, Shaul Mukamel, Sid Nagel, US National Science Foundation, Keith Nelson,
Kenji Ohmori, Takeshi Oka, Janine O’Guinn, Colleen O’Leary, April Oleson, Mrs.
Ruth Patterson, Barbara Perry, Fred Perry, David Picconi, David Pratt, Jim Prell,
Mike Raymer, Tom Record, Stuart Rice, Philip Richardson, Mary Rohrdanz, Victor
Romero-Rochin, Sandy Rosenthal, Sister Rosilda FSPA, Penny Salus, Marsha Saxton,
Rich Saykally, Norbert Scherer, Greg Scholes, Moshe Shapiro, Mike Sheahan, Yu-Chen
Shen, Nancy Shows, Robert J. Silbey (my postdoctoral advisor, a gem of a human be-
ing), Michael Sipe, Barbara Sklar, Martin Smith, Tim Smith, Peter Straton, Joe
Subotnik, Susie Cina Sullivan, David Tannor, Judithe Thompson, Nacho Tinoco, Dr.
Brandy Todd, Emma Tran, Daniel Turner, Rob Tycko, David Tyler, Lowell Ungar, my
fellow members of Oregon’s faculty labor union United Academics, Marian Valentine,
Steven van Enk, Hailin Wang, John Waugh, Bob Weiss, Julia Widom, Kevin Wiles,
Cathy Wong, Claude Woods, Duane C. Wrenn and Leticia Steuer of Energetic Soul,
John Wright, Joel Yuen-Zhou, Larry Ziegler.
Contents
1 Short-pulse electronic absorption 1

1.1 Basic set-up 1
1.2 Energy changes of molecule and field 2
1.3 Expectation values 3
1.4 The Heller formula 5
1.5 Systems starting in thermal equilibrium 6
1.6 Example absorption calculations 7
2 Adiabatic approximation 11
2.1 Molecular Hamiltonian 11
2.2 Molecular eigenstates 12
3 Transient-absorption spectroscopy: Making ultrashort pulses
worthwhile 17
3.1 Model Hamiltonian and signal expression 17
3.2 Transient-absorption dipole 20
3.3 Exemplary calculations 23
4 How fissors works: Femtosecond stimulated Raman spectroscopy
as a probe of conformational change 34
4.1 Basic idea 34
4.2 Signal formation 36
4.3 Fissors dipole 38
4.4 Example signal calculation 45
5 Transient-absorption reprise: Taking advantage of vibrational
adiabaticity 53
5.1 Transient-absorption signal under vibrational adiabaticity 53
5.2 Calculated transient-absorption signals 55
6 Two and a half approaches to two-dimensional wave-packet
interferometry 61
6.1 Introduction 61
6.2 Measured quantities 62
6.3 Quantum mechanical aspects 76
6.4 Example signals 85
7 Two-dimensional wave-packet interferometry for an electronic
energy-transfer dimer 96
7.1 Energy-transfer dimer 96
7.2 Whoopee signal 99
xii Contents
7.3 Illustrative calculations 105

Appendix A Electromagnetic energy change due to light ab-
sorption 129
Appendix B Delay regions for doubly excited-state-visiting over-
laps in the difference-phased singly excited-state populations 131
Appendix C Delay regions for overlaps contributing to the difference-
phased doubly excited-state population 135
Index 137
1
Short-pulse electronic absorption
1.1 Basic set-up

This chapter treats the interaction between an individual molecule, whose fixed lo-
cation is regarded as the spatial origin, and a short pulse of light. The molecule
may be isolated or immersed in a condensed-phase environment, but is assumed to
have an energetically isolated electronic transition at or near resonance with the in-
cident laser pulse. The time-dependent Hamiltonian of such a system can be written
H(t) = H + V (t), where
H = |giHg hg| + |ei( + He )he| , (1.1)
and
V (t) = −m̂ · E(t) . (1.2)
Hg and He are the nuclear Hamiltonians governing all relevant intra- and intermolec-
ular degrees of freedom in the ground and excited electronic states, respectively, and
is the “bare” electronic transition energy. The electric dipole-moment operator1 is

m̂ = m |eihg| + |gihe| , (1.3)
and the electric field of the pulse is assumed to take the form
E(t) = eEf (t) cos(Ωt + ϕ) , (1.4)
at the molecule’s location, with polarization e, pulse envelope f (t) peaked at t = 0

with approximate temporal width σ, carrier frequency Ω, and unspecified optical phase
ϕ.
The molecular state evolves according to
d 1
|Ψ(t)i = H(t)|Ψ(t)i , (1.5)
dt i~
with the initial condition
|Ψ(t 0)i = [t]|gi|ng i = |gi[t]gg |ng i = |gi|ng ie−itng /~ . (1.6)
We have adopted the notation

1 The electronic transition moment m may depend on nuclear coordinates in general, but we make
a “Condon approximation” by neglecting this possibility for the present.
2 Short-pulse electronic absorption
[t] ≡ exp{−iHt/~} and [t]gg ≡ hg| exp{−iHt/~}|gi = exp{−iHg t/~} , (1.7)

and |ng i is a nuclear eigenket in the electronic ground state obeying Hg |ng i = ng |ng i.
We shall seek a perturbative solution through second order in V , which can be written
abstractly as
|Ψ(t)i = |0i + | ↑i + | ↑↓i . (1.8)
Here |0i = [t]|gi|ng i for all times; explicit formulas for | ↑i = |eihe|Ψ(t)i and | ↑↓i ∼
∼ =
|gihg|Ψ(t)i − |0i will be developed shortly.
1.2 Energy changes of molecule and field

In pulsed absorption, the molecular system experiences a change in energy
∆E = hΨ(t 0)|H|Ψ(t 0)i − hΨ(t 0)|H|Ψ(t 0)i
∼
= h↑ |H| ↑i + h0|H| ↑↓i + h↑↓ |H|0i
= h↑ |H| ↑i + 2Reh0|H| ↑↓i . (1.9)
By energy conservation, it must be that ∆E + ∆U = 0, where ∆U is the accompa-
nying energy change of the electromagnetic field, calculated to the same order in V .
The electromagnetic energy change results from interference between the propagating
incident field and the electric field E(t) radiated by the oscillating dipole it induces in
the molecule:
Z
1
d3 s (E(t) + E(t))2 − E 2 (t)

∆U =
4π
Z
∼ 1
= d3 s E(t) · E(t) ; (1.10)
2π
E(t) in this expression is obtained from that in eqn (1.4) by replacing t with t − u · s/c,
where u is a unit vector in the propagation direction and s = sn locates the field-point.
The radiated dipolar field is given by
1
m̈(t − sc ) × n × n

E(t) = 2
c s
1
= − 2 (1 − nn) · m̈(t − sc ) ; (1.11)
c s
the double dots denote a second derivative with respect to time, and integration in
eqn (1.10) is over the saucer-like spatial region where the two fields overlap, depicted
in Fig. 1.1. The time-dependent dipole in eqn (1.11) is
m(t) = hΨ(t)|m̂|Ψ(t)i = 2Reh0|m̂| ↑i , (1.12)
through first order in the external field. If we take z to be the direction of incidence of
the laser pulse and x to be its polarization direction, then the energy change becomes
Z ∞
∆U = −EΩ dτ f (τ ) sin(Ωτ + ϕ)mx (τ ) ; (1.13)
−∞
this conversion from spatial to temporal integration is carried out in Appendix A.

Expectation values 3
x,y
~ct
~cσ
Fig. 1.1 Disk-shaped region of overlap between the propagating laser pulse and the induced
dipolar field from a molecular source at the origin. Electromagnetic interference between these
fields accounts for the light pulse’s energy change due to its interaction with the molecule.
As hinted by the physically suggestive form of eqn (1.13), there is a direct route
to this formula by way of a basic one for the rate of change of the molecular energy.
In general, one has
dE d
= hΨ(t)|H(t)|Ψ(t)i = h dΨ dΨ dH
dt |H(t)|Ψi + hΨ|H(t)| dt i + hΨ| dt |Ψi . (1.14)
dt dt
Using | dΨ 1
dt i = i~ H(t)|Ψi and H(t) = H + V (t), this becomes dE/dt = hΨ|dV /dt|Ψi;
the well-known statement that the time derivative of the expectation value of the
Hamiltonian equals the expectation value of the Hamiltonian’s time derivative. In the
present instance, we have
dE dE(t)
=− · hΨ(t)|m̂|Ψ(t)i ∼
= EΩf (t) sin(Ωt + ϕ)mx (t) , (1.15)
dt dt
which, together with energy conservation, returns eqn (1.13) upon integration, irre-
spective of the order in E to which the induced dipole is approximated.
1.3 Expectation values

In order to relate ∆E and ∆U to the underlying quantum mechanical molecular dynam-
ics, we need formulas for the zeroth-, first-, and second-order contributions to the time-
dependent state (1.8). The corresponding interaction-picture ket, |Ψ̃(t)i ≡ [−t]|Ψ(t)i,
obeys
d 1 1
|Ψ̃(t)i = [−t] − H + H + V (t) |Ψ(t)i = Ṽ (t)|Ψ̃(t)i , (1.16)
dt i~ i~
with Ṽ (t) = [−t]V (t)[t], subject to the initial condition |Ψ̃(t 0)i = |gi|ng i. The
1
Rt
formal solution, |Ψ̃(t)i = |gi|ng i + i~ −∞
dτ Ṽ (τ )|Ψ̃(τ )i, can be iterated to obtain a
second-order approximation,

|Ψ̃(t)i = 1 + P (t; τ ) + P (t; τ )P (τ ; τ̄ ) |gi|ng i , (1.17)
1
Rt
where P (t; τ ) ≡ i~ −∞
dτ Ṽ (τ ).2
For an electronically resonant or near-resonant field, it is a good approximation
to neglect highly oscillatory terms in P ’s integrand (i.e., to make a rotating-wave
approximation) and write
P (t; τ ) = iF |eihg|e−iϕ p(eg) (t; τ ) + |gihe|eiϕ p(ge) (t; τ ) ,

(1.18)
where F ≡ Eσe · m/2~, and

Z t
dτ
p(eg)
(t; τ ) ≡ [−τ ]ee [τ ]gg f (τ )e−iΩτ (1.19)
−∞ σ
is a reduced pulse propagator ; here [t]ee = he|[t]|ei = exp{−i( + He )t/~}. It follows

from this definition that p(ge) = (p(eg) )† .
Using this notation in eqn (1.17) and reverting to the Schrödinger picture yield
|Ψ(t)i = |gi[t]gg 1 − F 2 p(ge) (t; τ )p(eg) (τ ; τ̄ ) |ng i

+ |eiiF e−iϕ [t]ee p(eg) (t; τ )|ng i , (1.20)
whence |0i = |gi[t]gg |ng i (as stated above),
| ↑i = |eiiF e−iϕ [t]ee p(eg) (t; τ )|ng i , (1.21)
and
| ↑↓i = −|giF 2 [t]gg p(ge) (t; τ )p(eg) (τ ; τ̄ )|ng i . (1.22)
The reduced pulse propagator p(eg) is evidently responsible for shaping the e-state
nuclear wave packet generated from |ng i in the e ← g transition, while the nested
combination p(ge) p(eg) sculpts the second-order wave packet in the g-state.
Upon substituting these forms in eqn (1.9), we find
∆E = F 2 hng | p(ge) (∞; τ )( + He ) p(eg) (∞; τ̄ )|ng i

− 2F 2 Rehng |Hg p(ge) (∞; τ ) p(eg) (τ ; τ̄ )|ng i
= 2F 2 Rehng | p(ge) (∞; τ )( + He ) − Hg p(ge) (∞; τ ) p(eg) (τ ; τ̄ )|ng i ;

(1.23)
the observation time has been set to infinity because the energy increment stops chang-
ing after the end of the laser pulse. Notice that the molecular energy change is indepen-
dent of the optical phase ϕ, as we should expect under the conditions considered here.
The first term in the last member of eqn (1.23) accounts for the energy gained by pop-
ulation transfer to the electronic excited state, while the second tracks the energetic
consequence of ground-state “bleaching” (i.e., the loss of g-state population).
2 The τ appearing after the semicolon in P (t; τ ) is not an argument of the pulse propagator,
but simply identifies its integration variable. This notation proves useful in writing nested pulse
propagators like those appearing in the second-order term of eqn (1.17).
The Heller formula 5
For the change in electromagnetic energy (1.13) on the other hand, we have
Z ∞
∆U = −EΩmx dτ f (τ ) sin(Ωτ + ϕ)
−∞
× 2Re iF e−iϕ hng |[−τ ]gg [τ ]ee p(eg) (τ ; τ̄ )|ng i .

(1.24)
Within the rotating-wave approximation, this formula reduces to
∆U = −2F 2 ~Ω Rehng |p(ge) (∞; τ )p(eg) (τ ; τ̄ )|ng i

= −F 2 ~Ω hng |p(ge) (∞; τ )p(eg) (∞; τ̄ )|ng i , (1.25)
which relates the field’s energy loss to the center frequency of the laser pulse and the
squared norm of the nuclear wave packet it generates in the excited electronic state.
R∞
Use p(ge) (∞; τ )( + He ) − Hg p(ge) (∞; τ ) = −∞ dτ d
iΩτ
σ i~ dτ [−τ ]gg [τ ]ee e f (τ ) along
with integration by parts to verify once again, acknowledging approximations, that
∆E = −∆U, as required by energy conservation.
1.4 The Heller formula

We can explore the effect of pulse duration by adopting a specific, Gaussian form
f (τ ) = exp{−τ 2 /2σ 2 } for the envelope function. If we write
Z ∞
dτ ∞ dτ̄
Z
i
∆E = ~ΩF 2 f (τ )f (τ̄ )hng | e− ~ (+He −ng −~Ω)(τ −τ̄ ) |ng i , (1.26)
−∞ σ −∞ σ
and introduce new integration variables T = (τ + τ̄ )/2 and t = τ − τ̄ , we then find

Z ∞
√ dt iΩt i
∆E = ~ΩF π2
e hng | e− ~ (+He −ng )t |ng i exp{−t2 /4σ 2 } . (1.27)
−∞ σ
In the continuous-wave (cw) limit (σ longer than the inverse of the frequency spacing
between adjacent vibronic levels), eqn (1.27) becomes Heller’s celebrated expression
for the molecular electronic absorption spectrum as a Fourier transform of the time-
dependent overlap between a propagating e-state nuclear wave packet and the g-state
wave function from which it originates.3
Equation (1.27) can be formally evaluated for shorter pulses (lower spectral reso-
lution) by using e-state nuclear eigenkets obeying He |ne i = ne |ne i to obtain
2
X
∆E = 2π~ΩF 2 |hne |ng i|2 exp{− σ~2 ( + ne − ~Ω − ng )2 } . (1.28)
ne
As in the cw case, however, it is often more fruitful to evaluate ∆E by treating the

wave-packet overlap in Heller’s formula under short-time, semiclassical, or system-
bath-decomposition approximations. Reduced pulse propagators themselves can often
3 Eric J. Heller, The Semiclassical Way to Dynamics and Spectroscopy (Princeton University Press,
Princeton, 2018).
be handled with a variety of approximations relying on the brevity of ultrashort laser

pulses relative to the timescale of nuclear dynamics.
1. Derive eqn (1.28) from eqn (1.27) by inserting the stated vibronic completeness
relation and carrying out the resulting Gaussian integration.
2. Repeat this derivation,
P Pstarting instead
R ∞ from the final form in eqn (1.25) and
i τ~ (+ne −~Ω−ng )
using p(eg) (∞, τ ) = ne ng |ne ihng | −∞ dτ
σ f (τ )e .
1.5 Systems starting in thermal equilibrium

In the treatment given so far, the initial state of the target system together with its
environment is described “microcanonically,” taking it to be of a specified-energy form
proportional to |gi|ng i. In this approach, the pulsed-absorption signal, along with the
nonlinear optical signal expressions to be developed in subsequent chapters, is given
as hng |Ô|ng i, where Ô is a specified nuclear coordinate operator expressible in terms
of wave-packet-reshaping reduced pulse propagators and episodes of evolution under
the nuclear Hamiltonians associated with one or more electronic states; eqns (1.23)
and (1.25) both have this structure.
It is to be appreciated that the signal formulas derived in this manner are much
more general than the microcanonical set-up might seem to suggest. For the initial
nuclear state |ng i is assumed to be an eigenstate of Hg (not necessarily the ground
state) and this Hamiltonian can be regarded as governing both “system” and “envi-
ronmental” nuclear degrees of freedom: the former would comprise the translational,
orientational, and internal vibrational modes of a target chromophore and may also
include some nuclear degrees of freedom belonging to its immediate surroundings,
while the latter would consist of the nuclear degrees of freedom of the remainder of
the molecular environment.
If the system-environment boundary is defined spatially, for instance, and is set
far enough away from the target chromophore that sound waves emanating from this
molecule due to pulse-induced electronic transitions and the accompanying nuclear
dynamics cannot propagate to the boundary and back on the overall timescale of
the measurement (perhaps several tens of picoseconds), then the relevant portion of
the nuclear operator Ô = Ôsys ⊗ Ienv pertains to the system alone. Reduced pulse
(eg)
propagators, in particular, take simplified forms such as p(eg) = psys ⊗ Ienv to an
excellent approximation, as the same condition automatically applies to the duration
of any incident laser pulse. The signal can then be written as
hng |Ô|ng i = Trsys [Ôsys ρ̂sys ] , (1.29)
where the quantum mechanical trace is taken over system degrees of freedom and
ρ̂sys = Trenv [ |ng ihng | ] is the system density operator expressed as a trace over envi-
ronmental degrees of freedom of the microcanonical distribution.
If the “environment” is sufficiently large and sufficiently weakly coupled to the
system that it becomes equivalent, as regards the statistical properties of the system,
to a heat bath at some absolute temperature T, then the initial density operator of
(sys)
the system will take the canonical form ρ̂sys = Z −1 exp{−Hg /kB T }. Here Z =
Example absorption calculations 7
(sys)
Trsys [e−Hg /kB T ] is the partition function of the system and kB is the Boltzmann
constant. In this way, any of the optical signal expressions investigated here can be
readily translated into the corresponding finite-temperature Boltzmann-weighted form.
A handy shortcut is to regard the |ng i themselves as nuclear eigenstates of a
subsystem in weak contact with a temperature reservoir. Then the thermally weighted
sum of individual signal contributions hng |Ô|ng i reduces to Tr[Ôρ̂], with
ρ̂ = Z −1 ng |ng ie−ng /kB T hng |, or Tr[Ôρ̂] = Z −1 ng e−ng /kB T hng |Ô|ng i.
P P
1.6 Example absorption calculations

We can illustrate some basic features of pulsed linear absorption by investigating a
model one-dimensional system with potential-energy curves reminiscent of a diatomic
molecule embedded in a solid medium. The nuclear Hamiltonians in eqn (1.1) are
p2x
taken to be Hg(e) = 2m + Vg(e) (x), where
mω 2 2
Vg (x) = x − αx3 + βx4 (1.30)
2
and Ve (x) = Vg (x − xe ). Here α = ~ω/32x3rms and β = ~ω/860x4rms , with xrms =
p
~/2mω. We set the wave number of the harmonic vibration to 200 cm−1 , which
corresponds to a period of τx = 2π/ω = 166.8 fs. The spatial shift of the e-state
potential is assigned the value xe = 2.626xrms , so the classical inner turning point at
an energy 2e lies at x = 0, directly above the g-state minimum. It is not necessary to
specify a value for the vibrational reduced mass m. Fig. 1.2 shows the two potential-
energy curves. The bare electronic transition energy in eqn (1.1) is given an arbitrary
wave number of 20, 000 cm−1 .
1200
1000
V(x) (cm-1 )
800
Vg(x) Ve(x)
600
400
200
0
0 5 10 15
x/xrms
Fig. 1.2 Potential curves governing nuclear motion in the g- and e-states of the one-dimen-
sional model Hamiltonian. Ve does not include the bare electronic transition energy.
For this simple system, it is a straightforward numerical exercise to solve for the
eigenvalues and eigenstates of both nuclear Hamiltonians and to obtain position repre-
sentations of the latter, using a harmonic-oscillator basis for instance. Matrix elements
of the reduced pulse propagators can also be easily determined. The absorption spec-
trum can then be evaluated as a function of the carrier frequency for any incident pulse
duration, using either eqn (1.25) or eqn (1.28). The spectrum for σ = 5τx starting from
the initial state |g|0g , shown in Fig. 1.3, is of sufficient resolution clearly to discern
individual vibronic transitions. The absolute value of the corresponding Heller kernel
appearing in the integrand of eqn (1.27) is plotted in the same figure, and reflects the
complicated wave-packet dynamics that ensues upon the abrupt promotion of |0g to
the e-state potential. It exhibits quasi-harmonic motion for a couple vibrational pe-
riods, after which wave-packet spreading in Ve (x) born of anharmonicity gives rise to
less regular temporal evolution in the overlap. The kernel’s overall amplitude decays
on a timescale set by the pulse-duration parameter σ.
~ (✏+He ✏0g )t |0g i]

#%! #%!
!%( !%(
!%' i !%'
Abs[h0g | e
!%& !%&
!%$ !%$
2
t2 /4
!%! !%!
e
! "!! #!!! #"!! $!!! ! " #! #" $!
ℏΩ!ϵ ")*!! # !!τ!
Fig. 1.3 On the left is the absorption spectrum for the 1D model, calculated for the case of
narrow-bandwidth σ = 5τx pulses of continuously variable center frequency. The dimension-
less field-strength parameter F is chosen so that the highest (1e ← 0g ) peak has unit intensity.
The right panel shows the absolute value of the temporal overlap function, which provides a
wave-packet-dynamical description of the absorption process.
The absorption spectrum of the same system at temperature T = 298 K, with the
same pulse duration and field strength, is plotted as a solid line in Fig. 1.4. While the
spectral resolution is unchanged, the Boltzmann-weighted distribution of population
over initial levels with ng = 0, 1, . . . leads to the appearance of new peaks at various
ne ← 1g , 2g , . . . transition frequencies. The resolution is degraded with the use of
wider-bandwidth, σ = 0.5τx pulses. The resulting linear absorption spectrum of the
model system in the ng = 0 state is shown as the dashed line in Fig. 1.4.
The spectra in Figs 1.3 and 1.4 illustrate several key ideas. The quasi-cw absorp-
tion of this relatively simple system provides detailed information on the energy eigen-
spectrum and the Franck–Condon overlaps ne |ng , and is amenable to a dynamical
description through the Heller kernel. In more complicated, multi-mode systems, how-
ever, thermal congestion and the presence of many closely spaced energy levels make it
more difficult to resolve individual vibronic transitions. Short-pulse linear absorption,
on the other hand, pays for its temporally well-localized excitation with a correspond-
ing loss of spectral resolution. In a one-pulse experiment, this loss of resolution in the
frequency domain remains uncompensated by improved temporal resolution resulting
from precise control of the timing within a sequence of individual light-matter interac-
tions. As is explored in subsequent chapters, strategies have been developed to address
Example absorption calculations 9
1.0
0.8
0.6
0.4
0.2
0.0
0 500 1000 1500 2000
- (cm-1 )
Fig. 1.4 Solid line is the absorption spectrum of the model at room temperature, again with
σ = 5.0τx . Dashed curve gives the spectrum starting from ng = 0, with σ = 0.5τx .
this conundrum by systematically varying the delay between excitation and probing
in several different forms of ultrafast nonlinear optical spectroscopy.

Fig. 1.5 Nuclear wave packets in the electronic excited state of the model system at t = 0
(top) and 0.5753τx (bottom). The legend identifies the long, intermediate, and short values
of the pulse-duration parameter σ used in these calculations
.
Figure 1.5 illustrates the dynamics initiated by pulses of differing duration in the
model molecule. It shows wave packets in the position representation,
ψe (x, t) ≡ x|e−i(He −2e )t/ p(eg) (∞; τ )|0g , (1.31)
at t = 0 and 0.5753τx (about half the period of vibrational motion at energy 2e ), with
center frequency Ω = ( + 2e − 0g )/. The upper panel plots the real part of ψe (x, 0).
For the longest pulse-length, σ = 2.0τx , this initial wave packet closely resembles the
stationary wave function hx|2e i. The shortest pulse, with σ = 0.2τx , essentially copies
hx|0d i into the excited electronic state. Each of these wave packets after half a period of
evolution, along with one generated by a pulse of intermediate duration, is illustrated
in the lower panel. The longest-pulse packet remains almost unchanged, while that
generated by the shortest pulse migrates to larger distance and is distorted by motion
in the anharmonic e-state potential. It is ultrashort laser pulses’ capacity to initiate
and interrogate wave-packet dynamics that underlies their usefulness in time-resolved
nonlinear optical spectroscopy.
2
Adiabatic approximation
2.1 Molecular Hamiltonian

The fact that atomic nuclei tend, as a result of their greater mass, to move more slowly
than electrons do undergirds many basic features of molecular structure and dynamics.
In particular, it motivates the ubiquitous Born–Oppenheimer, or adiabatic approxi-
mation, which greatly simplifies the quantum mechanical description of stationary and
nonstationary molecular states. In this chapter, we describe the molecular adiabatic
approximation and spell out the conditions for its validity.1 In succeeding chapters, we
will encounter additional applications of the quantum mechanical adiabatic theorem,
which can be invoked whenever there is a clear timescale separation between relevant
molecular degrees of freedom.
The time-independent Schrödinger for a molecule takes the general form
(TN + Te + Vee + VeN + VN N )|Ψi = E|Ψi , (2.1)
in which the Hamiltonian operator is the sum of five terms:
X P̂α · P̂α
TN =
2Mα
nuclei α
is the nuclear kinetic energy operator,

X p̂i · p̂i
Te =
2m
electrons i
is the electronic kinetic energy,

XX e2
Vee =
i j>i
|r̂i − r̂j |
is the repulsive, electron-electron Coulombic potential energy,

X X (−Zα e)e
VeN =
i α |r̂i − R̂α |
1 Some of the arguments in this section follow those made in Chap. 21 of Gordon Baym, Lectures
on Quantum Mechanics (Westview Press, New York, 1990).
12 Adiabatic approximation
is the attractive, electron-nuclear Coulombic interaction, and

X X (−Zα e)(−Zβ e)
VN N =
α β>α |R̂α − R̂β |
is the repulsive, nucleus-nucleus Coulombic interaction.

The ratio of electron mass to nuclear mass is typically m/M ∼ 10−4 to 10−5 .
Typical electronic momenta are of size h/λdeBroglie ∼ ~/a, where a is the molecu-
lar size, so successive electronic energy levels are separated by about ∼ ~2 /ma2 , or
several electron volts. If a nucleus were displaced by the full molecular size a from
its equilibrium position, the energy would change by an amount on the order of this
electronic transition energy. Regarding the nuclear motion as roughly harmonic, then,
M ω 2 a2 ∼ ~2 /ma2 , which implies
m 1/2 ~2
~ω ∼ . (2.2)
M ma2
Vibrational excitation energies are thereby found to be a smaller than electronic en-
ergies by a factor (m/M )1/2 ∼ 10−2 . Additionally, since the nuclear kinetic energy is
of size P 2 /2M ∼ ~ω/2, nuclear momenta are roughly
1/4 1/4
M ~ M
P ∼ ∼ p. (2.3)
m a m
Thus nuclear momenta are about ten times larger than electronic momenta, and nu-
clear speeds P/M are one thousand times smaller than electronic speeds. Finally, the
typical deviation of a nuclear position from its equilibrium average value is given by
M ω 2 δ 2 /2 ∼ ~ω/2, which leads to the estimate (δ/a)2 ∼ (m/M )1/2 , or
m 1/4
δ∼ a; (2.4)
M
the spatial range of zero-point nuclear motion is about one-tenth the range of electronic
motion (i.e., one-tenth the “molecular size”). These ballpark figures support a physical
picture of a molecule as a well-defined configuration of nuclei executing slow, small
amplitude oscillations around their equilibrium positions within a delocalized medium
of rapidly moving electrons.
Make a physical argument estimating molecular rotational excitation energies rela-

tive to vibrational and electronic energies.
2.2 Molecular eigenstates

Since the nuclei are well localized compared with the electrons—and much more slowly
moving—while the nuclear excitation energies are a small fraction of electronic ener-
gies, we are led to regard the nuclear kinetic energy operator TN as a perturbation
and seek solutions to the electronic Schrödinger equation which obey
Molecular eigenstates 13
(Te + Vee + VeN + VN N )|ϕn (R̂)i = En (R̂)|ϕn (R̂)i . (2.5)
The electronic eigenkets are parametrized by the nuclear coordinate operators, which
we symbolically denote by R̂ = (R̂1 , R̂2 , . . . ). The electronic eigenenergies En (R̂) like-
wise depend on the locations of the nuclei.
We can relate the nuclear-coordinate-operator-dependent electronic eigenkets to
those at some reference nuclear arrangement—say the equilibrium configuration in
the electronic ground state—by a unitary tranformation:
|ϕn (R̂)i = U (R̂)|ϕn i . (2.6)
The electronic unitary operator U (R̂) is actually a large collection of different unitary
operators parametrized by R̂. Since the reference eigenkets |ϕn i constitute a complete
orthonormal set in the electronic state-space, we could P seek molecular eigenkets as
expansions in this fixed electronic basis of the form n |ϕn i|Θn i, where the |Θn i are
nuclear states. But it proves more useful by far to look for energy eigenstates of the
combined electronic and nuclear degrees of freedom as expansions in the adiabatic
electronic basis: X X
|Ψi = |ϕn (R̂)i|Φn i = U (R̂) |ϕn i|Φn i . (2.7)
n n
Justification for the adiabatic electronic basis as the practical choice emerges when
we substitute |Ψi in the molecular Schrödinger equation (2.1) and take account of the
small ratio of electronic to nuclear mass.
Making this substitution and availing ourselves of the electronic Schrödinger equa-
tion (2.5) lead to
Xh i X
TN + Em (R̂) |ϕm (R̂)i|Φm i = E |ϕm (R̂)i|Φm i . (2.8)
m m
Taking the inner product of eqn (2.8) with |ϕn (R̂)i yields a set of coupled equations
for the nuclear states {|Φn i}:
h i X
hϕn (R̂)|TN |ϕn (R̂)i + En (R̂) |Φn i + hϕn (R̂)|TN |ϕm (R̂)i|Φm i = E|Φn i . (2.9)
m6=n
Let us examine the operator coupling nuclear kets associated with different electronic
states, which can be rewritten as
X P̂α · P̂α
hϕn (R̂)|TN |ϕm (R̂)i = hϕn |U † (R̂) U (R̂)|ϕm i
α
2Mα
X1
= hϕn | U † (R̂)P̂α U (R̂) · U † (R̂)P̂α U (R̂)|ϕm i
α
2M α
X 1 h i h i
= hϕn | P̂α + Aα (R̂) · P̂α + Aα (R̂) |ϕm i , (2.10)
α
2Mα
where the induced vector potential Aα (R̂) = −i~U † (R̂)∇α U (R̂) is an operator in the
electronic state-space parametrized by the nuclear coordinate operators.2 Now
X 1
hϕn (R̂)|TN |ϕm (R̂)i = hϕn |ϕm i P̂α · P̂α
α
2Mα
X 1
+ P̂α · hϕn |Aα (R̂)|ϕm i + hϕn |Aα (R̂)|ϕm i · P̂α
α
2Mα
X 1
+ hϕn |Aα (R̂) · Aα (R̂)|ϕm i . (2.11)
α
2Mα
The inner product hϕn |ϕm i equals δnm . The matrix elements of the vector potential,
hϕn |Aα (R̂)|ϕm i = −i~hϕn (R̂)|∇α ϕm (R̂)i, are of estimated size ~/a as one would have
to move the αth nucleus a molecule-sized distance to produce near unit overlap between
a given adiabatic electronic state and another to which it had been orthogonal. The
second sum on the right-hand side of eqn (2.11) therefore contains terms of order
3/4
p2

~ m
Pα ∼ ,
Mα a m Mα
a thousand times smaller than electronic excitation energies. Terms in the third sum
are of similar or smaller size,
1 1 X
hϕn |Aα (R̂) · Aα (R̂)|ϕm i = hϕn |Aα (R̂)|ϕl i · hϕl |Aα (R̂)|ϕm i
2Mα 2Mα
l
2
1 X ~ m p2
∼ ∼ 10 ,
2Mα a Mα 2m
l
assuming that ten states contribute significantly.

We see that the portions of TN coupling different electronic states are about one
one-thousandth of a standard electronic energy splitting. The corresponding pertur-
bative corrections to a molecular eigenstate3 go as
matrix element
∼ 10−3 ,
electronic energy difference
while corrections to the eigenenergy are of size
(matrix element)2 ~2
∼ 10−6 .
energy difference ma2
Except in the presence of degenerate or unusually closely spaced electronic energies,
both of these corrections should be negligibly small.
2 The ∂ ∂ ∂
gradient with respect to the αth nuclear coordinate is ∇α = i +j +k . In
∂Xα ∂Yα ∂Zα
evaluating ∇α U (R̂) it is to be understood that we first calculate ∇α U (R1 , R2 , · · · ) and then replace
(R1 , R2 , · · · ) with (R̂1 , R̂2 , · · · ).
3 See, for example, Chap. 5 of J. J. Sakurai, Modern Quantum Mechanics, Revised Edition
(Addison-Wesley, Reading, 1994).
Molecular eigenstates 15
We are led to adopt the Born–Oppenheimer approximation, under which the ex-
pansion in eqn (2.7) is reduced to a single term,4
|Ψi ∼
= |ϕn (R̂)i|Φn i . (2.12)
In this approximation, the nuclear state that accompanies |ϕn (R̂)i obeys the equation
h i
hϕn (R̂)|TN |ϕn (R̂)i + En (R̂) |Φn i = E|Φn i , (2.13)
whose eigenvalues are the approximate molecular eigenenergies.

Using eqn (2.11) with m set equal to n and writing
hϕn |Aα (R̂) · Aα (R̂)|ϕn i = hϕn |Aα (R̂)|ϕn i · hϕn |Aα (R̂)|ϕn i
X
+ hϕn |Aα (R̂)|ϕm i · hϕm |Aα (R̂)|ϕn i ,
m6=n
we can rewrite eqn (2.13) as

( )
X 1 h i h i
(n) (n) 0
P̂α + Aα (R̂) · P̂α + Aα (R̂) + En (R̂) |Φn i = E|Φn i , (2.14)
α
2Mα
where
†
A(n)
α (R̂) = −i~hϕn |U (R̂)∇α U (R̂)|ϕn i = −i~hϕn (R̂)|∇α ϕn (R̂)i (2.15)
is the adiabatic vector potential experienced by the αth nucleus in the nth electronic
state, and
X 1 X
En0 (R̂) = En (R̂) + hϕn |Aα (R̂)|ϕm i · hϕm |Aα (R̂)|ϕn i . (2.16)
α
2Mα
m6=n
The nonadiabatic correction to En (R̂) is typically minuscule, as outlined above for

hϕn |Aα (R̂) · Aα (R̂)|ϕm i/2Mα . The adiabatic vector potentials can often—but not
(n)
always5 —be made to vanish entirely: Aα (R̂) must be real, for
hϕ|∇ϕi = ∇ hϕ|ϕi −h∇ϕ|ϕi = −hϕ|∇ϕi∗

| {z }
1
is imaginary. If the electronic wave function hr1 , r2 · · · |ϕn (R̂)i can be chosen real,
(n)
as it most often can be, then hϕn (R̂)|∇α ϕn (R̂)i will be real. Hence Aα (R̂) is also
imaginary and therefore zero.
4 The Born–Oppenheimer-approximated state |Ψi is not, in general, a tensor product. Rather it is
a “sum” of products d3 R1 d3 R2 · · · |ϕn (R1 , R2 , · · · )i|R1 , R2 , · · · ihR1 , R2 , · · · |Φn i, in which the
R R
electronic state is correlated with the arrangement of the nuclei and weighted by the probability
amplitude, Φn (R1 , R2 , · · · ) = hR1 , R2 , · · · |Φn i, for the nuclei to have a particular arrangement.
5 M. V. Berry, “Quantal phase factors accompanying adiabatic changes,” Proc. R. Soc. Lond.
A392, 45–57 (1984).
When the dust settles, it is often sufficient to combine a solution of the simplified
nuclear wave equation, h i
TN + En (R̂) |Φn i = E|Φn i , (2.17)
in which the electronic eigenenergy as a function of nuclear coordinates acts as a

potential energy surface for the nuclear motion, with the adiabatic electronic state
|ϕn (R̂)i to obtain an approximate molecular eigenket with total energy (electronic
plus nuclear) equal to E.
1. How much can you figure out about the eigenstates and eigenenergies of the
model Hamiltonian
P12 + P22 M ω2 2
H= + (Q1 + Q22 ) + κQ1 σx + κQ2 σy ,
2M 2
where (Q1 , Q2 ) and (P1 , P2 ) are vibrational coordinates and momenta, respectively,
σx = |eihg| + |gihe| ,
σy = −i|eihg| + i|gihe| ,
and
σz = |eihe| − |gihe| ,
√
are Pauli operators in a two-dimensional electronic state-space, and κ = k ~M ω 3 ,
with a dimensionless constant k, is a coupling coefficient between electronic and
nuclear degrees of freedom?
2. In addition to determining the stationary nuclear wave functions, the approximate
Hamiltonian appearing in eqn (2.17) governs nuclear dynamics. Consider a one-
dimensional vibrational Hamiltonian,
P2 M ω2 2
T + E(X) = + X ,
2M 2
where [X, P ] = i~. Investigate the time-dependent expectation value and mean-
square deviation of X and P in a Glauber coherent state specified by the initial
condition |Φi = e−iP̂ X◦ /~ |0i, where X◦ is some initial displacement and |0i is the
ground state of this harmonic nuclear Hamiltonian.
Two references pertinent to the first of these exercises are given below.6
6 H. C. Longuet-Higgins, U. Öpik, M. H. L. Pryce, and R. A. Sack, “Studies of the Jahn-Teller

effect. II. The dynamical problem,” Proc. R. Soc. Lond. A 244, 1–16 (1958); J. C. Slonczewski and
V. L. Moruzzi, “Excited states in the dynamic Jahn-Teller effect,” Physics 3, 237–254 (1967).
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Valley of the Nile was regarded as a direct violation of the
rights of Egypt and Great Britain, and that, in accordance
with my instructions, I must protest in the strongest terms
against their occupation of Fashoda, and their hoisting of the
French flag in the dominions of His Highness the Khedive. In
reply, M. Marchand stated that as a soldier he had to obey
orders; the instructions of his Government to occupy the
Bahr-el-Ghazal and the Mudirieh of Fashoda were precise, and,
having carried them out, he must await the orders of his
Government as to his subsequent action and movements. I then
pointed out that I had the instructions of the Government to
re-establish Egyptian authority in the Fashoda Mudirieh, and I
asked M. Marchand whether he was prepared—on behalf of the
French Government—to resist the execution of these orders; he
must be fully aware, I said, that the Egyptian and British
forces were very much more powerful than those at his
disposal, but, at the same time, I was very averse to creating
a situation which might lead to hostilities. I therefore
begged M. Marchand to most carefully consider his final
decision on this matter. I further informed him that I should
be pleased to place one of the gun-boats at his disposal to
convey him and his expedition north. In answer to this, M.
Marchand did not hesitate to admit the preponderating forces
at my disposal, and his inability to offer effective armed
resistance; if, however, he said, I felt obliged to take any
such action, he could only submit, to the inevitable, which
would mean that he and his companions would die at their
posts. He begged, therefore, that I would consider his
position, and would allow the question of his remaining at
Fashoda to be referred to his Government, as, without their
orders, he could not retire from his position or haul down his
flag; at the same time, he said he felt sure that, under the
circumstances, the orders for his retirement would not be
delayed by his Government, and that then he hoped to avail
himself of the offer I had made him. I then said to him: 'Do I
understand that you are authorized by the French Government to
resist Egypt in putting up its flag and reasserting its
authority in its former possessions—such as the Mudirieh of
Fashoda?' M. Marchand hesitated, and then said that he could
not resist the Egyptian flag being hoisted. I replied that my
instructions were to hoist the flag, and that I intended to do
so. … The Egyptian flag was hoisted … at 1 P. M. with due
ceremony in the presence of the British and Egyptian troops,
and a salute of twenty-one guns was fired.
{200}
I should add that, in the course of the conversation, I
informed M. Marchand that, in addition to my verbal protest, I
intended to make a formal protest in writing, and this I duly
handed him before leaving Fashoda. During these somewhat
delicate proceedings nothing could have exceeded, the
politeness and courtesy of the French officers. Having
officially appointed Major Jackson Commandant of the Fashoda
district, and leaving with him a battalion of infantry, four
guns, and a gun-boat, I proceeded south with the remainder of
the troops and four gun-boats. …
"I had no opportunity for a further interview with M.

Marchand, who, I venture to think, holds at Fashoda a most
anomalous position—encamped with 120 men on a narrow strip of
land, surrounded by marshes, cut off from access to the
interior, possessing only three small boats without oars or
sails and an inefficient steam-launch which has lately been
dispatched on along journey south, short of ammunition and
supplies, his followers exhausted by years of continuous
hardship, yet still persisting in the prosecution of his
impracticable undertaking in the face of the effective
occupation and administration of the country I have been able
to establish. It is impossible not to entertain the highest
admiration for the courage, devotion, and indomitable spirit
displayed by M. Marchand's expedition, but our general
impression was one of astonishment that an attempt should have
been made to carry out a project of such magnitude and danger
by the dispatch of so small and ill-equipped a force which—as
their Commander remarked to me, was neither in a position to
resist a second Dervish attack nor to retire—indeed, had our
destruction of the Khalifa's power at Omdurman been delayed a
fortnight, in all probability he and his companions would have
been massacred. The claims of M. Marchand to have occupied the
Bahr-el-Ghazal and Fashoda Provinces with the force at his
disposal would be ludicrous did not the sufferings and
privations his expedition endured during their two years'
arduous journey render the futility of their efforts
pathetic."
Great Britain, Parliamentary Publications

(Papers by Command: Egypt, Numbers 2 and 3, 1898).
The "Fashoda incident," as it was described, caused great

excitement in both England and France, and threatened for some
weeks to involve the two countries in war. Both army feeling
and popular feeling in France very nearly forced the
government to persist in what was plainly an ill-considered
and inopportune movement, and to hold untenable ground. But
better sense prevailed, and, on the 2d of November, when the
Sirdar, Lord Kitchener, who had visited England, was being
feasted and given the freedom of London, at Guildhall, Lord
Salisbury was able to make a dramatic announcement of the
closing of the dispute. "I received," he said, speaking at the
banquet, "from the French ambassador this afternoon the
information that the French Government had come to the
conclusion that the occupation of Fashoda was of no sort of
value to the French Republic, and they thought that, under
those circumstances, to persist in an occupation which only
cost them money and did them harm, merely because some
people—some bad advisers—thought it might be disagreeable to
an unwelcome neighbor, would not show the wisdom with which, I
think, the French Republic has been uniformly guided, and they
have done what I believe many other governments would have
done in the same position—they have resolved that the
occupation must cease."
EGYPT: A. D. 1898-1899.
The Gordon Memorial College at Khartoum.
On an appeal from Lord Kitchener, funds were raised in Great

Britain for the founding of a Gordon Memorial College at
Khartoum, to be, in the first instance, a school for
elementary instruction to the sons of the heads of districts
and villages.
EGYPT: A. D. 1898-1901.
The Barrage and Reservoir works on the Nile.
In February, 1898, the Khedive in Council approved a contract

concluded with the British firm of John Aird & Company, for
the construction of a dam or "barrage" across the Nile at
Assouan, drowning the cataracts and turning the river above
into a vast storage reservoir; with another dam at Assiout,
for the irrigation of Middle Egypt and the Fayum. In the
report of Lord Cromer for 1898, Sir William Garstein, at the
head of the Egyptian Public Works Department, gave the
following description of the plan of the works, then fairly
under way: "The dam which is to form the reservoir will be
built at the first cataract, a few miles south of Assouan. It
is designed to hold up water to a level of 106 metres above
mean sea level, or rather more than 20 metres above the
low-water level of the Nile at site. Its total length will be
2,156 yards with a width at crest of 26.4 feet. The width of
base at the deepest portion will be 82.5 feet, and the height
of the work at the deepest spot will be 92.4 feet. The dam
will be pierced by 180 openings, or under-sluices (140 of
which are 23.1 feet by 6.6 feet and 40 are 18.2 feet by 6.6
feet) provided with gates. These sluices will pass the flood
and surplus water through the dam, and by them the reservoir
will be emptied when water is required for irrigation in
Middle and Lower Egypt. Three locks will be built, and a
navigation channel made on the west of the river to enable
boats to pass up and down.
"The dam at Assiout will be what is called an open Barrage,
and will be similar in construction to the existing Barrages
on the Rosetta and Damietta branches. The new work will
consist of 111 bays or openings, each 16.5 feet wide, and each
bay will be provided with regulating gates. The total length
of the work will be 903 yards. A lock 53 feet in width will be
constructed on the west bank, large enough to pass the largest
tourist boat plying on the river. By regulating on this
Barrage water will be supplied in spring and summer to the
Ibrahimieh Canal, which irrigates Middle Egypt. At present
this canal has to be dredged to a depth of some 2 metres below
the lowest summer level in the river, and even with these the
crops suffer in years of low summer supply. A regulation
bridge with a lock will be built at the head of the Ibrahimieh
Canal in order to allow of the supply being reduced, if
necessary, in flood."
Great Britain, Papers by Command: Egypt,

Number 3, 1899.
By a singular happening, the Nile flood of 1899 was the lowest

recorded in the century, and gave an opportunity for the
barrage and irrigation works, barely begun as they were, to
give a convincing foretaste of their value. According to the
report of that year, "the distress was enormously less than on
all previous occasions of a failure of the flood. The area of
'sharaki,' or land unirrigated and therefore untaxed, which
had been 900,000 feddans in 1877 was only one-third of this in
1899.
{201}
Even in this area, which lay principally in Upper Egypt,
'distress,' says Sir William Garstein, 'was hardly felt at all
by the people. The immense amount of contract work in progress
in the country enabled them to obtain a good daily wage and
tided over the interval between the two crops.' In Lower Egypt
'the situation was saved by the Barrage, which, for the first
time in its history, was regulated upon throughout the flood.
Had it not been for the work done by this structure, there is
little doubt that large areas of crop would have been lost. As
it is, the cotton crop is very nearly the largest on record,
and the maize crop was up to the average.'" Of the progress of
the work at Assouan it is said: "After nearly a year had been
spent in accumulation of material and various preparations,
the foundation stone of the dam was laid by H. R. H. the Duke
of Connaught on February 12; and from that date the work was
carried on with less interruption than must have been
necessitated by a normal flood. Beginning on the east bank,
masonry was carried on throughout a length of 620 metres, and
of these, 360 metres were brought up to within two metres of
their full height. … Not less satisfactory progress was made
with the weir at Assiut, although the original design had to
be considerably altered."
On the 7th of February, 1901, a Press despatch from Cairo

reported: "Sir John Aird and Sir Benjamin Baker start for
England on Sunday next, having completed their visit of
inspection to the great engineering works at Assuan, where the
immense dam to hold up the waters of the Nile is being
constructed. The total extent of the dam is one mile and a
quarter, of which one mile and an eighth of the foundation is
finished. Temporary dams enabling the remaining section to be
put in are now carried across the channel. Pumps for getting
in the permanent dam foundations will be started next week.
The whole of the granite masonry required for the dam is cut
and ready to be laid in its place. The parapet alone remains
to be prepared. The portion of the dam remaining to be built
is that across the well-known deep western channel. The work
is of considerable difficulty, but the experience gained last
season in dealing with other channels has rendered the
engineers and contractors confident that equal success will be
obtained this year in the western channel. The dam is pierced
with 180 openings, about 23 feet high and 7 feet wide, which
openings are controlled by steel sluices. The work for the
latter is now well advanced. The discharge through these
sluices at high Nile may reach 15,000 tons of water per
second. The navigation channel and chain of locks are equally
advanced with the dam itself, and the lock gates will also be
in course of construction in about three months. Unless
anything unforeseen occurs the reservoirs will be in operation
for the Nile flood of 1903. This will be well within the
contract time, although owing to the increased depth of the
foundations the work done by the contractors has been largely
increased.
"At Assiut the great regulating dam across the Nile approaches
completion, the foundations being practically all in position,
leaving a portion of the superstructure to be completed. The
sluice openings here number 119, all 16 feet wide. This dam is
somewhat similar in principle to the well-known barrage near
Cairo, but the details of construction are entirely different,
as the foundations are guarded against undermining by a
complete line of cast iron and steel-piling above and below
the work. The barrage itself is constructed of high-class
masonry instead of brickwork as at the old barrage. Although
the Assiut barrage is overshadowed by the greater magnitude of
the Assuan dam, it will, doubtless, rank second as the
monumental work of Egypt."
EGYPT: A. D. 1899 (January).

The Anglo-Egyptian Condominium established in the Sudan.
The following agreement between the British government and

that of the Khedive of Egypt, relative to the future
administration of the Sudan, establishing a condominium or
joint dominion therein, was signed at Cairo on the 19th of
January, 1899, and made public the same day:
Whereas certain provinces in the Sudan which were in rebellion

against the authority of His Highness the Khedive have now
been reconquered by the joint military and financial efforts
of Her Britannic Majesty's Government and the Government of
His Highness the Khedive; and whereas it has become necessary
to decide upon a system for the administration of and for the
making of laws for the said reconquered provinces, under which
due allowance may be made for the backward and unsettled
condition of large portions thereof, and for the varying
requirements of different localities; and whereas it is
desired to give effect to the claims which have accrued to Her
Britannic Majesty's Government by right of conquest, to share
in the present settlement and future working and development
of the said system of administration and legislation; and
whereas it is conceived that for many purposes Wadi Haifa and
Suákin may be most effectively administered in conjunction
with the reconquered provinces to which they are respectively
adjacent; now, it is hereby agreed and declared by and between
the Undersigned, duly authorized for that purpose, as follows:
ARTICLE I.
The word "Sudan" in this Agreement means all the territories
South of the 22nd parallel of latitude, which:
1. Have never been evacuated by Egyptian troops since the year

1882; or
2.
Which, having before the late rebellion in the Sudan been
administered by the Government of His Highness the Khedive,
were temporarily lost to Egypt, and have been reconquered by
Her Majesty's Government and the Egyptian Government acting in
concert; or
3. Which may hereafter be reconquered by the two Governments

acting in concert.
ARTICLE II.
The British and Egyptian flags shall be used together, both on
land and water, throughout the Sudan, except in the town of
Suákin, in which locality the Egyptian flag alone shall be
used.
ARTICLE III.
The supreme military and civil command in the Sudan shall be
vested in one officer, termed the "Governor-General of the
Sudan." He shall be appointed by Khedivial Decree on the
recommendation of Her Britannic Majesty's Government, and
shall be removed only by Khedivial Decree, with the consent of
Her Britannic Majesty's Government.
{202}
ARTICLE IV.
Laws, as also Orders and Regulations with the full force of
law, for the good government of the Sudan, and for regulating
the holding, disposal, and devolution of property of every
kind therein situate, may from time to time be made, altered,
or abrogated by Proclamation of the Governor-General. Such
Laws, Orders, and Regulations may apply to the whole of any
named part of the Sudan, and may, either explicitly or by
necessary implication, alter or abrogate any existing Law or
Regulation. All such Proclamations shall be forthwith notified
to Her Britannic Majesty's Agent and Consul-General in Cairo, and
to the President of the Council of Ministers of His Highness
the Khedive.
ARTICLE V.
No Egyptian Law, Decree, Ministerial Arrêté, or other
enactment hereafter to be made or promulgated shall apply to
the Sudan or any part thereof, save in so far as the same
shall be applied by Proclamation of the Governor-General in
manner hereinbefore provided.
ARTICLE VI.
In the definition by Proclamation of the conditions under
which Europeans, of whatever nationality, shall be at liberty
to trade with or reside in the Sudan, or to hold property
within its limits, no special privileges shall be accorded to
the subjects of anyone or more Power.
ARTICLE VII.
Import duties on entering the Sudan shall not be payable on
goods coming from Egyptian territory. Such duties may,
however, be levied on goods coming from elsewhere than
Egyptian territory, but in the case of goods entering the
Sudan at Suákin, or any other port on the Red Sea Littoral,
they shall not exceed the corresponding duties for the time
being leviable on goods entering Egypt from abroad. Duties may
be levied on goods leaving the Sudan at such rates as may from
time to time be prescribed by Proclamation.
ARTICLE VIII.
The jurisdiction of the Mixed Tribunals shall not extend, nor
be recognized for any purpose whatsoever, in any part of the
Sudan, except in the town of Suákin.
ARTICLE IX.
Until, and save so far as it shall be otherwise determined, by
Proclamation, the Sudan, with the exception of the town of
Suákin, shall be and remain under martial law.
ARTICLE X.
No Consuls, Vice-Consuls, or Consular Agents shall be
accredited in respect of nor allowed to reside in the Sudan,
without the previous consent of Her Britannic Majesty's
Government.
ARTICLE XI.
The importation of slaves into the Sudan, as also their
exportation, is absolutely prohibited. Provision shall be made
by Proclamation for the enforcement of this Regulation.
ARTICLE XII.
It is agreed between the two Governments that special
attention shall be paid to the enforcement of the Brussels Act
of the 2nd July 1890, in respect to the import, sale, and
manufacture of fire-arms and their munitions, and distilled or
spirituous liquors.
Done in Cairo, the 19th January, 1899.

(Signed) Boutros Ghali-Cromer.
A. S. White, The Expansion of Egypt,

Appendix V. (New York: New Amsterdam Book Company)
By a subsequent, agreement signed July 10, the exceptions in

the above relative to Suákin were abrogated.
EGYPT: A. D. 1899-1900.
Final defeat and death of the Khalifa.
Capture of Osman Digna.
Condition of the Sudan.
The Khalifa, who escaped from the scene of his overthrow at

Omdurman, in 1898, kept a following of his own tribe, the
Baggaras, sufficient to give trouble for more than another
year. At length, late in November, 1899, he was overtaken by
Sir Francis Wingate, who succeeded General Kitchener as
Governor-General of the Sudan, and was killed in a battle
fought near Gedil. Again Osman Digna, his able lieutenant,
escaped; but in January of the following year the latter was
captured and taken to Suez.
In a report to Lord Salisbury, made on the 20th of February,

1900, Lord Cromer, British Agent and Consul-General in Egypt,
gave the following account of the general state of affairs in
the Sudan:
"The territorial situation may be briefly described as

follows:—The frontier between the Soudan and the Italian
Colony of Erythræa has now been delimitated from Ras Kasar, on
the Red Sea, to Sabderat, a few miles east of Kassala.
Negotiations are proceeding which will, without doubt, result
before long in the delimitation of the small remaining portion
of the Italian frontier from Sabderat up to the point where it
strikes Abyssinian territory. The most friendly relations
exist between the British and Abyssinian Governments. The
general basis of a frontier arrangement in respect to the
country lying west of the Blue Nile has already been settled
with the Emperor Menelek. When the survey party, now being
employed, has finished its work, it may confidently be
expected that the detailed delimitation will be carried out
without much difficulty.
"An endeavour is being made to cut through the sudd which

obstructs the White Nile, and thus open up communication with
Uganda. To a certain extent this communication may be said to
be already established, for a mixed party, consisting of
British, French, and Belgian officers, with their followers,
arriving from the South, recently succeeded in getting through
and joining the Egyptian party, under Major Peake, which was
engaged in cutting the sudd. … From the moment of the
Khalifa's crushing defeat at Omdurman, the desert and Kordofan
tribes, with the exception of a certain number of Baggaras who
still adhered to the cause of their Chief, threw in their lot
with the Government. Most of these tribes, however, rendered
but little active assistance to the Government in the
subsequent operations against the Khalifa. Omdurman and the
Ghezireh [the tract of country lying south of Khartoum,
between the White and Blue Niles] were found to be full of
Arabs belonging to the Kordofan and far western tribes, who
had been brought from their homes by the Khalifa. They were
without any regular means of subsistence, but, in the existing
state of insecurity, it was for the time being impossible for
them to return to their own districts. … The inhabitants of
the districts which were raided by the Dervishes were obliged
to take refuge in the Ghezireh, with the result that the
situation remained practically unchanged until the Khalifa's
overthrow and death. Since then, the main objects of the
Government have been to send back to their homes the
inhabitants of the gum producing region, and to get rid of the
useless mouths from the Ghezireh. In respect to the first
point, some success has attended their efforts, but many
thousands of Arabs belonging to tribes whose homes are in
Kordofan and Darfour, still remain in the Ghezireh. … The
attitude of the Nubas and of other tribes in Central and
Southern Kordofan has, since the battle of Omdurman, been
perfectly satisfactory. … Some long time must certainly elapse
before prosperity returns to the tribes in the Soudan. The
population has wasted away under Dervish rule."
Great Britain, Papers by Command:

Egypt, Number 1, 1900, pages 43-44.
----------EGYPT: End--------
{203}
ELAM.
See (in volume 1)

BABYLONIA, PRIMITIVE;
(in volume 4)
SEMITES;
and (in this volume)

ARCHÆOLOGICAL RESEARCH: BABYLONIA, and PERSIA.
ELANDSLAAGTE, Battle of.
See (in this volume)

SOUTH AFRICA (THE FIELD OF WAR):
A. D. 1899 (OCTOBER-DECEMBER).
ELBE-RHINE CANAL PROJECT, The.

GERMANY: A. D. 1899 (AUGUST); and 1901 (JANUARY).
EL CANEY, Battle of.

UNITED STATES OF AMERICA: A. D. 1898 (JUNE-JULY).
ELECTRICAL SCIENCE, Recent advances in.

SCIENCE, RECENT: ELECTRICAL.
ELIZABETH, Empress of Austria:

Assassination.

AUSTRIA-HUNGARY: A. D. 1898 (SEPTEMBER).
EL ZANJON, Treaty of.

CUBA: A. D. 1868-1885.
EMPLOYERS' FEDERATION, British.

INDUSTRIAL DISTURBANCES; A. D. 1897.
EMPLOYERS' LIABILITY BILL, The English.

ENGLAND: A. D. 1897 (MAY-JULY).
EMPRESS-DOWAGER, of China, The.

CHINA: A. D. 1898 (OCTOBER), and after.
ENGINEERS, Strike and lockout of British.

INDUSTRIAL DISTURBANCES: A. D. 1897.
----------ENGLAND (GREAT BRITAIN): Start--------
ENGLAND: A. D. 1894.
The commandeering question with the South African Republic.

SOUTH AFRICA (THE TRANSVAAL): A. D. 1894.
ENGLAND: A. D. 1894-1895.
Retirement of Mr. Gladstone from public life.
Earl of Rosebery Prime Minister.
His speech on the "predominant member" and Home Rule.
Weakening and overthrow of the Liberal Government.
Dissolution of Parliament.
Conservative and Unionist triumph.
Third Ministry of Lord Salisbury.
Mr. Gladstone, who had passed his 84th year, whose health was
failing, and who might justly consider that his public work
was done, resigned his post as Prime Minister, on the 2d of
March, 1894, and the Earl of Rosebery, on his recommendation,
was called by the Queen to take his place. Slight changes,
otherwise, were made in the cabinet, but the spirit in the
Liberal government was no longer the same. The new Premier
soon signified that his disposition in the matter of Home Rule
for Ireland was not quite what Mr. Gladstone's had been, by
using the following language in a speech (March 13) in the
House of Lords:
"Before Irish Home Rule is conceded by the Imperial Parliament

England, as the predominant member of the partnership of the
three kingdoms, will have to be convinced of its justice. That
may seem to be a considerable admission to make, because your
lordships will know that the majority of English members of
Parliament, ejected from England proper, are hostile to Home
Rule. But I believe that the conviction of England in regard
to Home Rule depends on one point alone, and that is the
conduct of Ireland herself. I believe that if we can go on
showing this comparative absence of agrarian crime; if we can
point to the continued harmony of Ireland with the great
Liberal party of this country; if we can go on giving proofs
and pledges that Ireland is entitled to be granted that boon
which she has never ceased to demand since the Act of Union
was passed. I believe that the conversion of England will not
be of a slow or difficult character. My lords, the question of
Home Rule is one that I regard not from the point of view of
Ireland only. It has for me a triple aspect. It has, in the
first place, the aspect that I believe that Ireland will never
be contented until this measure of Home Rule be granted to
her; and that, though you may come in on other issues and
succeed us who sit here, your policy of palliatives is bound
to fail. In the second place, I believe that not merely have
we in our Irish policy to satisfy those who live in the island
of Ireland itself, encompassed, as Mr. Disraeli once said, by
that melancholy ocean, we have not merely to satisfy the Irish
themselves within Ireland, but, for the good of our Empire and
for the continuity and solidarity of our relations with our
brethren across the Atlantic, it is necessary that we should
produce an Irish policy which shall satisfy the Irish people.
And, lastly, I view it from the highest Imperial grounds,
because I believe that the maintenance of this Empire depends,
not on centralization, but on decentralization, and that if
you once commence to tread this path, you will have to give
satisfaction under the same conditions certainly to Scotland,
and possibly to Wales, not in the same degree or possibly in
the same way, but so as to relieve this groaning Imperial
Parliament from the burden of legislation under which it
labours. I will not detain you further on this subject
to-night. I did not mean to dilate so much on the question of
Home Rule."
His remarks seemed to show an intention to postpone the

pressing of the measure. Distrust arose among the Irish and
uncertainty was created in the mind of the Liberal party. It
became evident very quickly that the Liberals, with the loss
of their old leader, had lost heart and faith in the policy to
which he had committed them, and that a serious weakening of
the political energies of the party had been produced. No
measures which raised troublesome issues were undertaken in
Parliament during the year of Mr. Gladstone's retirement: but,
at the session which opened in the following February (1895), the
government brought forward a number of high]y important bills.
{204}
The first to be introduced was a bill "to terminate the

Establishment of the Church of England in Wales and Monmouth."
The bill made provision for the creation of a representative
Church body, giving power to the bishops, clergy and laity to
hold synods and to legislate on ecclesiastical matters. It
entrusted ecclesiastical revenues to a commission; provided
for the transfer of churches and parsonages to the
representative body of the Church, and of burial grounds and
glebes to parish, district, and town councils; other property
of the Church to be vested in the commission before mentioned,
which should also have the charge of cathedrals, to keep them in
repair. The bill had its first reading on the 28th of
February, and its second on the 1st of April, but went no
further. It shared the fate of the other measures of the
Government, including a bill to establish local control of the
liquor traffic, and others for the remedying of defects in the
Irish Land Law, and for the abolition of plural voting, all of
which were extinguished by the sudden and unexpected overthrow
of the Government on the 21st of June. It was defeated on a
motion to reduce the salary of the Secretary for War, which
was made for no purpose but to start a question as to the
adequacy of the provision of certain ammunition stored for
use. When the vote was found to be against the Government
there was great surprise in both parties. But the Ministry had
been steadily losing support and was quite willing to resign,
which it did the next day. Lord Salisbury was sent for by the
Queen and accepted the task of forming a new Government, with
the understanding that Parliament should be dissolved as soon
as practicable, and the will of the country ascertained. In
the new Government, Lord Salisbury filled the office of
Secretary of State for Foreign Affairs, with that of Prime
Minister; Mr. A. J. Balfour became First Lord of the Treasury;
Sir Michael Hicks-Beach Chancellor of the Exchequer; Mr.
Joseph Chamberlain Secretary of State for the Colonies; Mr. G.
J. Goschen First Lord of the Admiralty. Before the dissolution
of Parliament, which occurred on the 6th of July, a bill for
the amendment of the Factories Act, on which both parties
agreed, was passed. The elections that followed, beginning
July 13, resulted in the return of a majority of 152 in favor
of the new Ministry, which represented the coalition of
Conservatives and Liberal Unionists. The majority of the
popular vote on the same side in the three kingdoms was a
little more than 30,000, in a total poll of 4,792,512; but in
Eng]and the new Government received a majority of some
300,000. In Ireland the vote went heavily against them, and in
Wales and Scotland to a lighter extent. Of the Irish members
elected, 12 were of the Parnell faction and 69 Anti-Parnell.
The new Parliament came together August 12, and, after a brief
session, at which little was done, was prorogued September 5.
Enforcement of claims against Nicaragua.
CENTRAL AMERICA (NICARAGUA): A. D. 1894-1895.
The question of Chitral.

INDIA: A. D. 1895 (MARCH-SEPTEMBER).
ENGLAND: A. D. 1895 (January).

Agreement with France defining the boundaries of the
Hinterland of Sierra Leone.

SIERRA LEONE PROTECTORATE.
ENGLAND: A. D. 1895 (March-July).

Agreement with Russia concerning the northern Afghan frontier
and spheres of influence in the Pamir region.

AFGHANISTAN: A. D. 1895.
ENGLAND: A. D. 1895 (July-November).

Correspondence with the Government of the United States
on the Venezuela boundary question.

VENEZUELA: A. D. 1895 (JULY) and (NOVEMBER).
ENGLAND: A. D. 1895 (November).

Action on the closing of the Vaal River Drifts by the South
African Republic.

SOUTH AFRICA (THE TRANSVAAL):
A. D. 1895 (SEPTEMBER-DECEMBER).
ENGLAND: A. D. 1895 (December).
Message of the President of the United States to Congress
on the British Guiana-Venezuela boundary dispute.

VENEZUELA: A. D. 1895 (DECEMBER).
ENGLAND: A. D. 1895-1896 (November-January).

Discontent and revolutionary conspiracy of Uitlanders in
the Transvaal.
The Jameson Raid.

SOUTH AFRICA (THE TRANSVAAL): A. D. 1895 (NOVEMBER);
and A. D. 1895-1896.
ENGLAND: A. D. 1895-1896 (December-January).

The feeling in England and America over the
Venezuela boundary dispute.

UNITED STATES OF AMERICA:
A. D. 1895-1896 (DECEMBER-JANUARY).
Establishment of the Sierra Leone Protectorate.

SIERRA LEONE PROTECTORATE.
Report on Old-Age Pensions.
The question of the practicability and expediency of a

national system of pensions for old age, which had been
agitated in England for some years, and which a royal

Getting Started On Time Resolved Molecular Spectroscopy Jeffrey A Cina Full Chapter

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Getting Started on Time-Resolved

Molecular Spectroscopy Jeffrey A. Cina

1 Short-pulse electronic absorption 1

7.3 Illustrative calculations 105

1.1 Basic set-up

H = |giHg hg| + |ei( + He )he| , (1.1)

E(t) = eEf (t) cos(Ωt + ϕ) , (1.4)

at the molecule’s location, with polarization e, pulse envelope f (t) peaked at t = 0

|Ψ(t  0)i = [t]|gi|ng i = |gi[t]gg |ng i = |gi|ng ie−itng /~ . (1.6)

We have adopted the notation

[t] ≡ exp{−iHt/~} and [t]gg ≡ hg| exp{−iHt/~}|gi = exp{−iHg t/~} , (1.7)

1.2 Energy changes of molecule and field

this conversion from spatial to temporal integration is carried out in Appendix A.

1.3 Expectation values

P (t; τ ) = iF |eihg|e−iϕ p(eg) (t; τ ) + |gihe|eiϕ p(ge) (t; τ ) ,

where F ≡ Eσe · m/2~, and

is a reduced pulse propagator ; here [t]ee = he|[t]|ei = exp{−i( + He )t/~}. It follows

|Ψ(t)i = |gi[t]gg 1 − F 2 p(ge) (t; τ )p(eg) (τ ; τ̄ ) |ng i

+ |eiiF e−iϕ [t]ee p(eg) (t; τ )|ng i , (1.20)

whence |0i = |gi[t]gg |ng i (as stated above),

| ↑i = |eiiF e−iϕ [t]ee p(eg) (t; τ )|ng i , (1.21)

∆E = F 2 hng | p(ge) (∞; τ )( + He ) p(eg) (∞; τ̄ )|ng i

× 2Re iF e−iϕ hng |[−τ ]gg [τ ]ee p(eg) (τ ; τ̄ )|ng i .

Within the rotating-wave approximation, this formula reduces to

∆U = −2F 2 ~Ω Rehng |p(ge) (∞; τ )p(eg) (τ ; τ̄ )|ng i

1.4 The Heller formula

and introduce new integration variables T = (τ + τ̄ )/2 and t = τ − τ̄ , we then find

As in the cw case, however, it is often more fruitful to evaluate ∆E by treating the

be handled with a variety of approximations relying on the brevity of ultrashort laser

1.5 Systems starting in thermal equilibrium

1.6 Example absorption calculations

~ (✏+He ✏0g )t |0g i]

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ψe (x, t) ≡ x|e−i(He −2e )t/ p(eg) (∞; τ )|0g  , (1.31)

2.1 Molecular Hamiltonian

(TN + Te + Vee + VeN + VN N )|Ψi = E|Ψi , (2.1)

in which the Hamiltonian operator is the sum of five terms:

is the nuclear kinetic energy operator,

is the electronic kinetic energy,

is the repulsive, electron-electron Coulombic potential energy,

is the attractive, electron-nuclear Coulombic interaction, and

is the repulsive, nucleus-nucleus Coulombic interaction.

Make a physical argument estimating molecular rotational excitation energies rela-

2.2 Molecular eigenstates

(Te + Vee + VeN + VN N )|ϕn (R̂)i = En (R̂)|ϕn (R̂)i . (2.5)

|ϕn (R̂)i = U (R̂)|ϕn i . (2.6)

assuming that ten states contribute significantly.

whose eigenvalues are the approximate molecular eigenenergies.

we can rewrite eqn (2.13) as

The nonadiabatic correction to En (R̂) is typically minuscule, as outlined above for

hϕ|∇ϕi = ∇ hϕ|ϕi −h∇ϕ|ϕi = −hϕ|∇ϕi∗

in which the electronic eigenenergy as a function of nuclear coordinates acts as a

6 H. C. Longuet-Higgins, U. Öpik, M. H. L. Pryce, and R. A. Sack, “Studies of the Jahn-Teller

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Great Britain, Parliamentary Publications

The "Fashoda incident," as it was described, caused great

On an appeal from Lord Kitchener, funds were raised in Great

In February, 1898, the Khedive in Council approved a contract

Great Britain, Papers by Command: Egypt,

By a singular happening, the Nile flood of 1899 was the lowest

On the 7th of February, 1901, a Press despatch from Cairo

EGYPT: A. D. 1899 (January).

H = |giHg hg| + |ei( + He )he| , (1.1)

|Ψ(t 0)i = [t]|gi|ng i = |gi[t]gg |ng i = |gi|ng ie−itng /~ . (1.6)

is a reduced pulse propagator ; here [t]ee = he|[t]|ei = exp{−i( + He )t/~}. It follows

∆E = F 2 hng | p(ge) (∞; τ )( + He ) p(eg) (∞; τ̄ )|ng i

ψe (x, t) ≡ x|e−i(He −2e )t/ p(eg) (∞; τ )|0g , (1.31)