2015 Bookmatter AtomsMoleculesAndOpticalPhysic PDF

Appendices
Overview
These appendices offer a collection of concepts and relations which belong
to the standard mathematical ‘tools’ in atomic, molecular and optical physics.
On many occasions we refer to these in the main text. We do not attempt here
to derive them in a closed, axiomatic manner – rather a compact summary of
useful and important formulas and equations is presented. Usually they are
accompanied by some hints about their origins and connections to make them
plausible for the reader without requesting the substantial efforts needed to
go into the depth of derivations or proofs. Literature references are given for
further information.
Appendix A offers a tabulated overview of current values for the most important
physical constants used in atomic, molecular and optical physics – and in these
textbooks. Some remarks about systems of units and dimensional analysis are also
included.
Appendix B defines the angular momentum operators and introduces some ba-
sics about angular momentum algebra with 3j symbols (respectively C LEBSCH -
G ORDAN coefficients), 6j symbols (respectively R ACAH functions), and 9j sym-
bols.
Appendix C is concerned with the rules of evaluating and transforming matrix
elements of irreducible tensor operators. This includes the very important W IGNER -
E CKART theorem, matrix elements for electromagnetically induced transitions and
the reduction of coupling schemes as well as some useful geometrical relations.
Finally we give some directions for the evaluation of radial matrix elements.
Appendix D formulates the concept of parity and introduces – as an alternative
to the usual complex spherical harmonics – real basis states for angular momenta,
typically used in quantum chemistry. The concept is also extended to half integer
angular momenta.
Appendix E offers a recipe type of access to the important theme of coordinate
rotation for angular momenta and irreducible tensor operators.
550 Appendices
Appendix F introduces the concept of multipole expansions and gives the most
important relations derived from it. Two alternatives to define multipole tensor op-
erators are discussed: based on spatial coordinates and on combinations of angular
momentum operators.
Appendix G describes the concept of convolution and illustrates it for the most
important distribution functions.
Appendix I presents some essentials about F OURIER transformations with spe-
cial emphasis on electromagnetic fields.
Appendix H provides the formal basis for treating electromagnetically induced
transitions – are presented in the main text somewhat heuristically. It also derives
the important T HOMAS -R EICHE -K UHN sum rule.
In Appendix J, finally, we discuss the behaviour and the proper normalization of
continuum wave functions. Both are important for a correct treatment of ionization
and scattering processes.
Constants, Units and Conversions
A
A.1 Fundamental Physical Constants and Units
Modern physics relies on the knowledge of a relatively large number of so called

“fundamental constants” which are measured with high precision in an ongoing,
cooperative international effort. Table A.1 gives a survey on the most important
ones, used throughout these books.
Table A.1 2010 CODATA recommended values of physical constants extracted from NIST
(2010), published by M OHR et al. (2012)
Constant Value Equation
Universal constants
speed of light in vacuum c 2.99792458 × 108 m s−1 defined
magnetic constant μ0 4π × 10−7 N A−2 defined
107
electric constant ε0 8.854187817 . . . × 10−12 F m−1 1
μ0 c2
= 4π c2
characteristic vacuum Z0 376.730313461 . . . cμ0 = 1
impedance √ ε0 c
= μ0 /ε0
Newtonian constant of G 6.67384(80) × 10−11 m3 kg−1 s−2
gravitation G/c 6.70837(80) × 10−39 (GeV /c2 )−2
P LANCK constant h 6.62606957(29) × 10−34 J s
4.135667516(91) × 10−15 eV s
angular momentum quant 1.054571726(47) × 10−34 J s h/2π
c 197.3269631(49) MeV fm
√
P LANCK mass mP 2.17651(13) × 10−8 kg c/G
P LANCK length P 1.616199(97) × 10−35 m /(mP c)
P LANCK temperature TP 1.416833(85) × 1032 K mP c2 /kB
P LANCK time tP 5.39106(32) × 10−44 s P /c
Electromagnetic constants
elementary charge e 1.602176565(35) × 10−19 C
© Springer-Verlag Berlin Heidelberg 2015 551

I.V. Hertel, C.-P. Schulz, Atoms, Molecules and Optical Physics 1,
Graduate Texts in Physics, DOI 10.1007/978-3-642-54322-7
552 A Constants, Units and Conversions
Table A.1 (Continued)

B OHR magneton μB 927.400968(20) × 10−26 J T−1 e/(2me )
5.7883818066(38) × 10−5 eV T−1
μB / h 13.99624555(31) × GHz T−1
nuclear magneton μN 5.05078353(11) × 10−27 J T−1 e/(2mp )
3.1524512605(22) × 10−8 eV T−1
μN / h 7.622̇59357(17) MHz T−1
J OSEPHSON constant KJ 483597.870(11) × 109 Hz V−1 2e/ h
VON K LITZING constant RK 25812.8074434(84) Ω h/e2
Atomic and nuclear constants
electron mass me 9.10938291(40) × 10−31 kg
me 5.4857990946(22) × 10−4 u
electron g factora ge 2.00231930436153(53) μe μB
g factor anomaly ae 1.15965218073(28) × 10−3 g/2 − 1
proton mass mp 1.672621777(74) × 10−27 kg
proton-electron mass ratio me /mp 1836.15267245(75)
neutron mass mn 1.674927351(74) × 10−27 kg
mass of He nucleus mα 6.64465675(29) × 10−27 kg
unified atomic mass unit 1u 1.660538921(73) × 10−27 kg ≡ m(12 C)/12
atomic unit of energy Eh 27.21138505(60) eV e4 me /(4πε0 )2
atomic unit of length a0 0.52917721092(17) × 10−10 m 4πε0 2 /me e2
(B OHR radius) Eh a02 = 2 /me
RYDBERG constant R∞ 10 973 731.568539(55) m−1 Eh /(2hc)
atomic unit of time t0 2.418884326502(12) × 10−17 s /Eh
fine structure α 7.2973525698(24) × 10−3 e2 /(4πε
0 c)
constant 1/137.035999074(44) = Eh /me c2
new datab
1/137.035999037(91)
classical electron radiusc re 2.8179403267(27) × 10−15 m α 2 a0
C OMPTON wavelength λC 2.4263102389(16) × 10−12 m h/me c = 2παa0
T HOMSON cross section σe 0.665̇2458734(13) × 10−28 m2 (8π/3)α 4 a02
= (8π/3)re2
Proton radius Rp 0.8775(51) × 10−15 m
B OLTZMANN constant kB 1.3806488(13) × 10−23 J K−1
5 4
S TEFAN-B OLTZMANN σB 5.670373(21) × 10−8 W m−2 K−4 2 π kB
15 h3 c2
constant
AVOGADRO constant NA 6.02214129(27) × 1023 mol−1
molar volumed Vm 22.413953(21) × 10−3 m3 mol−1
L OSCHMIDT constantd NL 2.6516462(24) × 1025 m−3 NA /Vm
a.u. of dipole moment ea0 8.47835326(19) × 10−30 C m
A.2 SI and Atomic Units 553
Table A.1 (Continued)

energy equivalents 1 eV 1.602176565(35) × 10−19 J e × 1V
1J 6.24150934(14) × 1018 eV 1 J /1 eV
1u 0.931494061(21) GeV 1 u c2 /1 eV
me 0.510998928(11) MeV me c2 /1 eV
1 cm−1 1.239841930(27) × 10−4 eV hc/1 eV
eV in a.u. 1 eV 3.674932379(81) × 10−2 Eh 1 eV /2R∞ hc
eV in chem. units 1 eV 96̇.4853364(48) kJ mol−1 1 eV ×NA
−1
23.061 kcal mol
eV in wavenumbers 1 eV 8 065.54429(19) cm−1 1 eV / hc
eV in degree K 1 eV 1.1604519(11) × 104 K 1 eV /kB
a As usual in the literature, g is defined positive, see (1.164), in contrast to NIST
b By B OUCHENDIRA et al. (2011)
c This is just a constructed quantity: at this distance the C OULOMB energy of two electrons is equal
to the rest energy me c2 of an electron
d In ideal gas at 273.15 K and 100 kPa
A.2 SI and Atomic Units
In general, throughout these text books we consequently use the SI units, meter
(m), kilogram (kg), second (s), ampere (A), kelvin (K), mole (mol) and candela
(cd) – the international standard of units.
In addition to these 7 “base units” (NIST, 2000a, Table 1), we employ
• standard prefixes (NIST, 2000b), e.g. cm, mg, fs,

• SI “derived units” (NIST, 2000a, Tables 2 and 3) when useful or common cus-
tom, such as joule (J), volt (V) or degree Celsius (◦ C),
• several of the “accepted units outside the SI” (NIST, 2000c), such as electron-
Volt, 1 eV = e × V = 1.602 × 10−19 J, or barn, 1 b = 100 fm2 = 10−28 m2 . . . ,
• and make one exception for the occasionally used (non-SI) unit electron-barn,
1 eb = e × 1 b = 1.6022×10−47 A s m−2 .
We point out here that all values of constants and physical quantities given in the
table above and elsewhere in these text books refer to the currently valid definitions
of the SI. These definitions may possibly change in 2014 and be replaced by a new
set of definitions, completely based on fundamental constants (see Table A.1) as has
been decided by the CGPM (2011) (see also W IKIPEDIA CONTRIBUTORS, 2013).
Alternatively, we often use atomic units (a.u.) which are commonly used in
atomic and molecular physics. We consider these, however, to be just simplifying
abbreviations: one reformulates equations such, that for lengths, times and energies
only the combinations
r/a0 , t/t0 , and W/Eh , respectively, (A.1)
occur in the final expressions – which then become otherwise free of units and
include only some dimensionless parameters, such as the fine structure constant α.
It is often helpful to leave the equations in this form which simultaneously includes
a dimensional analysis. However, for simplicity of writing we occasionally omit the
respective units a0 , t0 , and Eh (e.g. in a S CHRÖDINGER equation), if no ambiguities
can arise. The respective quantities are then measured in a0 , t0 , and Eh . For more
details on a.u. see Sect. 1.8.3.
We emphasize, however, that it is rather misleading, to talk about “setting =
e = me = 1” – as occasionally formulated in (mostly theoretical) literature. The
same holds for relativistic expressions where the confusing notion that “one sets
c = 1” is often used – even in general texts, specifically on particle physics.
A.3 SI and GAUSS Units
The attentive reader will find a number of useful references to standard (mostly
older) and sometimes important literature, where G AUSS, electrostatic (esu) or elec-
tromagnetic (emu) units are still used (G AUSS units are equivalent to esu and emu
for electrostatic and electromagnetic units, respectively). Even in current literature,
specifically in theoretical papers, these systems are still used. Obviously, the seem-
ing advantage of writing a few equations in a simpler way than SI demands, ap-
pears so attractive to some authors that they renounce general compatibility. Thus,
Table A.2 communicates some conversion rules between the SI and the G AUSS
systems, following essentially the Appendix on units and dimensions in JACKSON
(1999).
A.4 Radian and Steradian
Radian (rad) and steradian (sr) are two somewhat ‘conspicuous’ units which are fre-
quently used in AMO physics. They are, however, genuine “SI derived units (NIST,
2000a)”. A brief clarification may be useful.
Radian and steradian may be visualized as shown in Fig. A.1. The radian (rad) is
defined in two dimensions for the plane angle ϕ by the length of an arc on a circle
of radius r, divided by this radius r:

ϕ= . (A.2)
r
With the full circumference of the circle being 2πr, the full angle thus becomes
ϕ = 2π rad = 360 ◦ , so that 1 rad = 360 ◦ /(2π) = 57.296 ◦ .
A.4 Radian and Steradian 555
Table A.2 Relations and conversions between the SI and the Gaussian system
Quantity/relation SI G AUSS
√
velocity of light c= 1/μ0 ε0 c
dielectric permittivity εr ε0 εr
magnetic permeability μr μ0 μr
electric field E, displacement D, D = ε0 E +√P = εr ε0 E D = E + 4πP √ = εr E
polarization P unit E esu = E SI 4πε0 E SI = E esu / 4πε0
magnetic H and B field, B = μ0 (H + M) B = H + 4πM √ = μr H
magnetization M unit = μr μ0 H √ B SI = B emu μ0 /4π
B emu = B SI 4π/μ0
M AXWELL equations ∇D = ρ ∇D = 4πρ
∇ × E = − ∂B
∂t ∇ × E = − 1c ∂B
∂t
∇B = 0 ∇B = 0
∇×H =J + ∂D
∂t ∇ × H = 1c (J + ∂D
∂t )
L ORENTZ force F = q(E + v × B) F = q(E + × B) v
c
√ √
charge, current, etc. q esu = q SI / 4πε0 q SI = √
4πε0 q esu
unit 1C = 1As 1esu =1 √dyn cm
√ √
=
2.9979 × 109 esu 4πε0 10−9 N m
=
= 3.3356 × 10−10 C
q1 q2 q1 q2
C OULOMB potential V (r) = 4π ε0 r V (r) = r
unit electric dipole moment Cm esu cm
D EBYE 1D = 3.33564 × 10−30 C m 1D = 10−18 esu cm
Polarizability esu = α SI /(4πε )
αE SI = (4πε )α esu
αE
E 0 0 E
B OHR magneton μB = e/(2me ) e/(2me c)
(a) (b)
rad = —
m
Fig. A.1 On the definition of (a) radian and (b) steradian
In three dimensions the steradian (sr) is defined as the solid angle Ω which char-
acterizes any surface area of the size S on a sphere of radius r. In other words, the
solid angle Ω is given as the surface S on a sphere of radius r divided by the square
of this radius:
S
Ω= . (A.3)
r2
For a cone with a full opening angle 2θ as shown in Fig. A.1 we have
θ
Ω= dΩ = 2π sin θ dθ = 2π(1 − cos θ ). (A.4)
0
With the surface of a sphere being 4πr 2 the full solid angle is 4π sr, and 1 sr cor-
responds to an angle θ = arccos(1 − 1/(2π)) = 0.57195 rad = 32.77◦ – or equiva-
lently to a cone with a full angle ϑ = 2θ = 65.54◦ .
Note that expressed in SI base units, both rad = m m−1 and sr = m2 m−2 have
the unit 1, i.e. are dimensionless. The symbols rad and sr may thus be used where
advantageous to distinguish the respective observable quantities from others . . . or
be omitted wherever the expressions are unambiguous.
For small angles (A.4) may be expanded as

lim Ω = πθ 2 + O θ 4 .
θ→0
The divergence of well collimated beams (light beams, electron or ion beams
etc.) is often given in mrad2 , i.e. in terms of the full divergence angle ϑ = 2θ mea-
sured in mrad. In the case of axially symmetry, i.e. for paraxial rays in a conical
beam, the solid angle of divergence is thus
2
π ϑ
Ω = 10−6 sr.
4 mrad
Thus, a (full) divergence angle of 1 mrad corresponds to a solid angle of Ω =
(π/4)10−6 sr. Note, however, that for a rectangular beam with a small diver-
gence ϑ 2 , measured in mrad2 , the solid angle is just Ω = 10−6 (ϑ/ mrad)2 sr.
A.5 Dimensional Analysis

In physics and technology dimensional analysis is often a useful tool to
• make a first check on the validity of a physical expression,

• guess, what the relation between several physical quantities might be,
• obtain orders of magnitude estimates from a given relation.
Throughout these textbooks we frequently make use of these possibilities. Thus, we

summarize here the terminology used in this context:
1. Physical quantities, such as the electron mass typically have
• a symbolic name, such as “me ”,

• a numerical value, here 9.1094 × 10−31 , and
Acronyms and Terminology 557
• a unit, here “kg”.

• Together we write for this quantity: me = 9.1094 × 10−31 kg.
2. In dimensional analysis we try to avoid specific units for mass, length, and so on,
since physical laws must be independent of the specific choice of units. Rather
we use a basic set of dimensions: mass (M), length (L), time (T), charge (Q),
and temperature () – all written in block letters without serifs. For most of our
purposes all other dimensions of physical quantities can be expressed as a prod-
uct of powers of these basic dimensions, e.g. the dimension of force is MLT−2 ,
of energy ML2 T−2 , of electric current QT−1 , or with the thermal energy being
Wtherm = kB T , the B OLTZMANN constant kB has the dimension ML2 T−2 −1
and so on.
3. However, for convenience or for clarity we shall sometimes use more letters or
abbreviations for the dimensions of physical quantities, e.g. for volume V = L3 ,
for energy Enrg = ML2 T−2 or R = L−3/2 for the dimension of a radial wave func-
tion.
4. The units of a physical quantity A or of a dimension A are represented by square
brackets, [A] and [A], respectively. For instance the unit of a potential V (r)
would be [V (r)] = eV – and more generally we have [Enrg] = eV or [Enrg] = J,
both are acceptable.
Acronyms and Terminology
AMO: ‘Atomic, molecular and optical’, physics.

a.u.: ‘atomic units’, see Sect. 2.6.2.
emu: ‘electromagnetic units’, old system of unities, equivalent to the G AUSS sys-
tem for magnetic quantities (see Appendix A.3).
esu: ‘electrostatic units’, old system of unities, equivalent to the G AUSS system for
electric quantities (see Appendix A.3).
NIST: ‘National institute of standards and technology’, located at Gaithersburg
(MD) and Boulder (CO), USA. http://www.nist.gov/index.html.
SI: ‘Système international d’unités’, international system of units (m, kg, s, A,
K, mol, cd), for details see the website of the Bureau International des Poids
et Mésure http://www.bipm.org/en/si/ or NIST http://physics.nist.gov/cuu/Units/
index.html.
References
B OUCHENDIRA, R., P. C LADE, S. G UELLATI -K HELIFA, F. N EZ and F. B IRABEN: 2011. ‘New
determination of the fine structure constant and test of the quantum electrodynamics’. Phys.
Rev. Lett., 106, 080801.
CGPM: 2011. ‘Resolution 1 of the General Conference on Weights and Measures (2011) CGPM:
On the possible future revision of the International System of Units, the SI’, Bureau Interna-
tional des Poid et Messure (BIPM). http://www.bipm.org/en/si/new_si/, accessed: 8 Jan 2014.
JACKSON, J. D.: 1999. Classical Electrodynamics. New York: John Wiley & sons, 3rd edn., 808
pages.
M OHR, P. J., B. N. TAYLOR and D. B. N EWELL: 2012. ‘CODATA recommended values of the fun-
damental physical constants: 2010’. Rev. Mod. Phys., 2013, 1527–1605. http://physics.nist.gov/
constants, accessed: 8 Jan 2014.
NIST: 2000a. ‘Reference on constants, units, and uncertainties: SI base and derived units’, NIST.
http://physics.nist.gov/cuu/Units/units.html, accessed: 8 Jan 2014.
NIST: 2000b. ‘Reference on constants, units, and uncertainties: SI prefixes’, NIST. http://physics.
nist.gov/cuu/Units/prefixes.html, accessed: 8 Jan 2014.
NIST: 2000c. ‘Reference on constants, units, and uncertainties: Units outside the SI’, NIST.
http://physics.nist.gov/cuu/Units/outside.html, accessed: 8 Jan 2014.
NIST: 2010. ‘Reference on constants, units, and uncertainties’, NIST. http://physics.nist.gov/
cuu/Constants/, accessed: 7 Jan 2014.
W IKIPEDIA CONTRIBUTORS: 2013. ‘Proposed redefinition of SI base units’, Wikipedia, The Free
Encyclopedia. http://en.wikipedia.org/wiki/Proposed_redefinition_of_SI_base_units, accessed:
8 Jan 2014.
Angular Momenta, 3j and 6j Symbols
B
We note here the most important relations for angular momenta in compact form
for reference and use throughout these books. Closely related are the 3j , 6j and 9j
symbols relevant for the coupling of angular momenta. They play an important role
in atomic and molecular physics. We follow here – with one important exception
concerning the normalization of the spherical components of angular momenta –
strictly the definitions of B RINK and S ATCHLER (1994) and E DMONDS (1996). Ex-
plicit expressions for the 3j , 6j and 9j symbols are somewhat complicated but well
documented in both references as well as in many textbooks on quantum mechan-
ics. For practical evaluation purposes one may use today readily accessible, compact
3j , 6j and 9j calculators (see e.g. S VEN G ATO R EDSUN, 2004). Also, they are of-
ten integrated in standard mathematical programmes. Thus, we refrain here from
extensive tabulations and restrict ourselves to definitions, symmetry properties, or-
thogonality relations, a few matrix elements and some important special cases (as
collected from several sources: E DMONDS, 1996; B RINK and S ATCHLER, 1994;
W EISSTEIN, 2004a,b).
B.1 Angular Momenta
B.1.1 General Definitions
The generalized angular momentum operator J is defined as vector operator with

three real, Hermitian components Jx , Jy and Jz with
Ji† = Ji for i = x, y, z, (B.1)
which satisfy the commutation relations

2
[Jx , Jy ] = iJz , [Jz , Jx ] = iJy , [Jy , Jz ] = iJx and
J , Ji = 0,
or in compact form:

560 B Angular Momenta, 3j and 6j Symbols

J ×
J = i
J and J ,
J = 0. (B.2)
Alternatively one may construct J from three spherical components J± and J0 (so
called helicity basis) which are an irreducible representation of the rotation group
of rank 1. They are derived from the real components:1
1 1
J+ = − √ (Jx + iJy ), J− = + √ (Jx − iJy ) and J0 ≡ Jz . (B.3)
2 2
The inverse relations are:
1 i
Jx = − √ (J+ − J− ), Jy = √ (J+ + J− ). (B.4)
2 2
We note that these operators are constructed in complete analogy to the spherical
components (4.75) of the position operator r in the helicity basis which we have
introduced in the context of dipole transitions in Sect. 4.4.
The spherical components J± are not Hermitian, with
J+† = −J− and J−† = −J+ , (B.5)
and their commutation relations are derived from (B.2):
[J0 , J± ] = ±J± and [J+ , J− ] = −J0 , (B.6)

2
2

J , J± = 0 and J , J0 = 0. (B.7)
J 1 and
The scalar product of two angular momenta J 2 is given by
J1 ·
J 2 = J1x J2x + J1y J2y + J1z J2z = −J1+ J2− + J10 J20 − J1− J2+ (B.8)
in accordance with the general definition of scalar products of tensor operators

(C.20). Hence,
2
J is expressed alternatively in the real or in the helicity basis:
+1

J = Jx2 + Jy2 + Jz2 = −J+ J− + J02 − J− J+ =
2
(−1)q Jq J−q . (B.9)
q=−1
The operators J+ and J− play a key role in the construction of angular mo-
mentum states. Using their commutation relations (B.6)–(B.7) one may construct
angular momentum states without using spherical harmonics (2.79)–(2.83) – which
1 Very often one finds in textbooks (even in B RINK and S ATCHLER, 1994) these ladder operators
defined as J± = Jx ± iJy . These are, however, not spherical components of the
J vector operator
and lead to asymmetric commutation relations. With the present definition – which is also used
e.g. by B LUM (2012), W EISSBLUTH (1978) – J± fulfill both functions: as ladder (or stepping)
operators and spherical components of J.
B.1 Angular Momenta 561
exclusively represent orbital angular momenta with integer quantum numbers . All
relevant algebra for angular momentum states may be derived in that way. Specifi-
cally, if |J M are eigenstates of Jz = J0 with eigenvalues M, it follows from (B.6)
that J+ |J M and J− |J M are also eigenstates of J0 with eigenvalues (M + 1) and
(M − 1), respectively:
J0 J± |J M = J± J0 |J M ± J± |J M

(B.10)
= (M ± 1)J± |J M.
With (B.7) the new states J± |J M are also eigenfunctions of

2
J . The operators
J+ and J− are thus raising and lowering operators (or ladder operators) for the
projection quantum number M. According to (B.10) M increases or decreases in
steps of one. One may show (here without proof) that M has a maximum and a
minimum value
−J ≤ M ≤ J, (B.11)
and clearly, this maximum and minimum value M = ±J can only be connected by
M = −J, −J + 1, . . . , J − 1, J if both M and J are either integer or half integer
numbers – in complete accordance with the experimental observation: integer values
arise from orbital angular momenta, and half integer values reflect the involvement
of spin 1/2 particles. The states thus generated obey the standard eigenvalue equa-
tions and are of orthonormalized:
2
J |J M = 2 J (J + 1)|J M and J0 |J M = M|J M (B.12)

J M J M = δJ J δM M . (B.13)
With some algebra one may show that the only nonvanishing matrix elements of the
spherical angular momentum components J0 , J+ and J− are

J M|J0 |J M = M and (B.14)

J M ± 1|J± |J M = ∓ √ a(±M) (B.15)
2

with a(M) = J (J + 1) − M(M + 1). (B.16)
Equivalently one may write:

J± |J M = ∓ √ a(±M)|J M ± 1 and J0 |J M = M|J M. (B.17)
2
We finally note, that all relations communicated in this section for the general
angular momentum J are completely equivalent to those for the orbital angular mo-
mentum L which we have derived in Sect. 2.5 (one may of course also introduce
spherical components L ± ). In contrast to L,
the general angular momentum is not
explicitly referring to position space and angles, and is not restricted to integer val-
ues of J and M.
B.1.2 Orbital Angular Momenta – Spherical Harmonics
One special kind of angular momenta are the orbital angular momenta introduced in
Sect. 2.5. As described there, their respective operators may be represented in terms
of spatial coordinates – more precisely, the operator of the squared orbital angular
momentum L and the components of
2
L can be expressed as differential operators
with respect to the azimuthal and polar angles in polar coordinates. Of particular
importance are

2 1 ∂ ∂ 1 ∂2
L = Lx + Ly + Lz = −
2 2 2 2
sin θ + 2 (B.18)
sin θ ∂θ ∂θ sin θ ∂ϕ 2
z = −i ∂
and L (B.19)
∂ϕ
with the spherical harmonics Ym (θ, ϕ) as joint eigenfunctions. These operators
have the eigenvalues 2 ( + 1) and m, respectively, corresponding to (B.12). Here
= 0, 1, 2, . . . and m is any integer value between − ≤ m ≤ .
Without proof we communicate here the spherical harmonics,

m 2 + 1 ( − m)! m
Ym (θ, ϕ) = (−1) P (cos θ ) exp(imϕ) (B.20)
4π ( + m)!
2π π
∗
with dϕ Ym (θ, ϕ)Y m (θ, ϕ) sin θdθ = δ δm m . (B.21)
0 0
Pm (x) are the associated L EGENDRE polynomials

m dm P (x) d+m 2
1 2 m
Pm (x) = 1 − x2 = 1 − x x −1 , (B.22)
dx m
2 ! dx +m
which in turn are derived from the ordinary L EGENDRE polynomials
1 d 2
P (x) =
x −1 . (B.23)
2 ! dx
As a function of cos θ the first L EGENDRE polynomials are:
P0 (cos θ ) = 1
P1 (cos θ ) = cos θ
3 1
P2 (cos θ ) = cos2 θ − (B.24)
2 2
5 3
P3 (cos θ ) = cos3 θ − cos θ
2 2
1
P4 (cos θ ) = 35 cos4 θ − 30 cos2 θ + 3 .
8
B.1 Angular Momenta 563
We also note the orthogonality relation

4π
P (cos θ )P (cos θ )dΩ = δ .
4π 2 + 1
With P0 (cos θ ) = 1 follows for all L EGENDRE polynomials with > 0

P (cos θ )dΩ = 0. (B.25)
4π
The definition (B.20) of the spherical harmonics Ym (θ, ϕ) implies the so called
standard phase convention according to C ONDON and S HORTLEY (1951) with the
factor (−1)m . One finds that the c.c. is
∗
Ym (θ, ϕ) = (−1)m Y−m (θ, ϕ), (B.26)
and inversion at the origin (r → −r) leads to
Ym (π − θ, π + ϕ) = (−1) Y−m (θ, ϕ). (B.27)
The spherical harmonics are said to have positive or negative parity depending on
whether is even or odd, respectively (see detailed discussion in Appendix D). In
compact form one obtains – well suited for computational use –

(−1)+m (2 + 1)( − m)! d+m (sin θ )2
Ym (θ, ϕ) = (sin θ )m exp(imϕ)

2 ! 4π( + m)! d(cos θ )+m

(−1) (2 + 1)( + m)! d−m (sin θ )2
= (sin θ )−m exp(−imϕ).
2 ! 4π( − m)! d(cos θ )−m
(B.28)
For simplicity of writing one often also uses renormalized spherical harmonics

4π
Cm (θ, ϕ) = Ym (θ, ϕ). (B.29)
2 + 1
We note the special values

Ym (0, ϕ) = (2 + 1)/(4π)δm,0 and Cm (0, ϕ) = δm,0 . (B.30)
Explicit expressions for the renormalized spherical harmonics up to = 3 are given

in Table B.1. A graphical illustration of their angular dependence is shown in
Fig. 2.6.
Table B.1 Spherical harmonics according to (B.28) and (B.29)

m Symbol 2 Renormalized
L Lz √spherical harmonics
Ck (θ, ϕ) = 4π/(2 + 1)Ym (θ, ϕ)
0 0 s 0 0 C00 = 1
1 0 p0 22 0 C10 = cos θ

±1 p±1 22 ± C1±1 = ∓ 12 sin θ · e±iϕ
2 0 d0 62 0 C20 = 12 (3 cos2 θ − 1)

±1 d±1 62 ± C2±1 = ∓ 32 sin θ cos θ · e±iϕ

±2 d±2 62 ±2 C2±2 = 38 sin2 θ · e±i2ϕ
3 0 f0 122 0 C30 = 12 (5 cos3 θ − 3 cos θ)

√
±1 f±1 122 ± C3±1 = ∓ 14 3e±iϕ sin θ(5 cos θ 2 − 1)

±2 122 ±2 C3±2 = 15 2 ±2iϕ
f±2 8 cos θ sin θ e
√
±3 f±3 122 ±3 C3±3 = ∓ 4
5
sin3 θ · e±3iϕ
B.2 Coupling of Two Angular Momenta: CLEBSCH-GORDAN

Coefficients and 3j Symbols
B.2.1 Definitions
When coupling two angular momenta

J 1 and
J 2 to generate a third one
J1 +
J2 =
J
the eigenstates |J M of the latter are constructed from the uncoupled states |J1 M1
and |J2 M2 as

|J1 J2 J M = |J1 M1 J2 M2
J1 M1 J2 M2 |J1 J2 J M. (B.31)
M1 M2

Formally, one may read the sum |J1 M1 J2 M2
J1 M1 J2 M2 | ≡ 1 simply as quan-
tum mechanical unit operator (see Sect. 2.3.1) written in front of |J1 J2 J M. J1 , J2
and J are the corresponding (integer or half integer) angular momentum quantum
numbers, M1 , M2 and M the corresponding projection quantum numbers in respect
of the z-axis. The inverse transformation is

|J1 M1 J2 M2 = |J1 J2 J M
J1 J2 J M|J1 M1 J2 M2 , (B.32)
JM
and the coefficients
J1 J2 J M|J1 M1 J2 M2 are the conjugate complex ones of
J1 M1 J2 M2 |J1 J2 J M. According to the general convention one chooses the phase
such that the coefficients are real:
J1 J2 J

J1 J2 J M|J1 M1 J2 M2 =
J1 M1 J2 M2 |J1 J2 J M = CM 1 M2 M
. (B.33)
B.2 Coupling of Two Angular Momenta 565
They are called C LEBSCH -G ORDAN coefficients. They are non-zero if – and only –
two conditions are fulfilled:
1. for the Ji quantum numbers δ(J1 J2 J ) = 1 must be fulfilled, with the triangular
relation defined by:

1 if |J2 − J1 |, |J2 − J1 | + 1, . . . ≤ J ≤ |J2 + J1 |
δ(J1 J2 J ) = (B.34)
0 else
2. for the projection quantum numbers Mi = M1 , M2 and M
−Ji , −Ji + 1, . . . ≤ Mi ≤ Ji and (B.35)

M = M1 + M 2
must hold.
The C LEBSCH -G ORDAN coefficients disappear if the triangular relation is not sat-
isfied, i.e. if δ(J1 J2 J ) = 0, or if M = M1 + M2 .
Alternative to the C LEBSCH -G ORDAN coefficients the W IGNER 3j symbols

J1 J2 J
M1 M2 M
are used. They are defined completely symmetric in respect of the three angular
momenta, and are related to the C LEBSCH -G ORDAN coefficients by

J1 −J2 +M J1 J2 J

J1 M1 J2 M2 |J M = (−1) (2J + 1)1/2
. (B.36)
M1 M2 −M
Note the minus sign in front of M in the last column. The 3j symbols disappear
unless
δ(J1 J2 J ) = 1 and M1 + M2 = M. (B.37)
B.2.2 Orthogonality and Symmetries
The following orthonormality relations hold:

J1 M1 J2 M2 J M
J1 M1 J2 M2 |J M = δM1 M δM2 M δ(J1 J2 J ) (B.38)
1 2
JM

J1 M1 J2 M2 J M
J1 M1 J2 M2 |J M = δMM δJ J δ(J1 J2 J ). (B.39)
M1 M2
Correspondingly, the 3j symbols satisfy the orthogonality relations:

J1 J2 J J1 J2 J
(2J + 1) = δM1 M δM2 M δ(J1 J2 J )
M1 M2 M M1 M2 M 1 2
JM
(B.40)
J1 J2 J

J1 J2 J

(2J + 1) = δJ J δMM δ(J1 J2 J ) (B.41)
M1 M2 M M1 M2 M
M1 M2
J1 J2 J
2
δ(J1 J2 J )
and thus also = . (B.42)
M1 M2 M (2J + 1)
M1 M2
The 3j symbols are symmetric in respect of cyclic exchange of their columns.

Their sign changes according to (−1)J1 +J2 +J when two columns are exchanged or
the sign of all projection quantum numbers is changed:

J1 J2 J J2 J J1 J J1 J2
= = (B.43)
M1 M2 M M2 M M1 M M1 M2

J2 J1 J
= (−1)J1 +J2 +J etc. (B.44)
M2 M1 M

J1 +J2 +J J1 J2 J
= (−1) . (B.45)
−M1 −M2 −M
B.2.3 General Formulae
The 3j symbols can be computed either by suitable recursion formulae or from the
R ACAH formula:

J1 J2 J
(B.46)
M1 M2 M

= (−1)J1 −J2 −M δ(M1 +M2 )−M (J1 J2 J )

× (J1 + M1 )!(J1 − M1 )!(J2 + M2 )!(J2 − M2 )!(J + M)!(J − M)!

× (−1)t t! (J − J2 + t + M1 )!(J − J1 + t − M2 )!
t
−1
× (J1 + J2 − J − t)!(J1 − t − M1 )!(J2 − t + M2 )!
with the so called triangular function
(a + b − c)!(a − b + c)!(−a + b + c)!

(abc) = . (B.47)
(a + b + c + 1)!
B.2 Coupling of Two Angular Momenta 567
One has to sum over all values of t which lead to non-negative terms for the faculty
expressions in (B.47). The 3j symbols can be obtained very fast from simple com-
puting programmes, as already mentioned (e.g. S VEN G ATO R EDSUN, 2004, Java
script, also for 6j and 9j symbols).
B.2.4 Special Cases
Closed expressions for some frequently used cases are often useful. The 3j symbol
becomes specially simple if one of the angular momenta is zero:

J1 J2 0 (−1)J1 −M1 δJ1 J2 δ−M1 M2
= √ . (B.48)
M1 M2 0 2J1 + 1
From (B.45) one finds the rule:

J1 J 2 J
= 0 if S = J1 + J2 + J is odd. (B.49)
0 0 0
A rather compact expression is also obtained if S = J1 + J2 + J is even and all

projection quantum numbers are zero:
1/2
J1 J2 J (S − 2J1 )!(S − 2J2 )!(S − 2J )!
= (−1)S/2 (B.50)
0 0 0 (S + 1)!
(S/2)!
× .
(S/2 − J1 )!(S/2 − J2 )!(S/2 − J )!
Frequently used relations are:

J+ 1
J 1
J −M−1/2 J − M + 1/2
2 2 = (−1) (B.51)
M −M − 1
2
1
2
(2J + 1)(2J + 2)

J +1 J 1 (J − M)(J − M + 1)
= (−1)J −M−1 (B.52)
M −M − 1 1 (2J + 1)(2J + 2)(2J + 3)

+1 J 1 2(J − M + 1)(J + M + 1)
= (−1)J −M−1 (B.53)
M −M 0 (2J + 1)(2J + 2)(2J + 3)

J J 1 (J − M)(J + M + 1)
= (−1)J −M (B.54)
M −M − 1 1 J (2J + 1)(2J + 2)

J J 1 M
= (−1)J −M √ (B.55)
M −M 0 J (J + 1)(2J + 1)

J J 2
(B.56)
M−M − 2 2

6(J − M − 1)(J − M)(J + M + 1)(J + M + 2)
= (−1)J −M
(2J + 3)(2J + 2)(2J + 1)2J (2J − 1)

J J 2
(B.57)
M −M − 1 1

6(J + M + 1)(J − M)
= (−1)J −M (1 + 2M)
(2J + 3)(2J + 2)(2J + 1)2J (2J − 1)

J J 2 2[3M 2 − J (J + 1)]
= (−1)J −M √ . (B.58)
M −M 0 (2J + 3)(2J + 2)(2J + 1)2J (2J − 1)
Note: Formula (B.54) is slightly erroneous in B RINK and S ATCHLER (1994).
B.3 RACAH Function and 6j Symbols

B.3.1 Definition
Often one has to couple three angular momenta. A typical case is the hyperfine
structure (HFS) of atoms in one electron systems, where orbital angular momentum,
electron spin and nuclear spin have to be considered. In the case of two electrons,
one may have no orbital angular momentum (ns orbital), the other electron may
be in a n configuration, e.g. Hg(6sn). Here the spins of the two electrons cou-
ple to a total spin and the latter couples with the orbital angular momentum of the
n electron. In molecular physics too, a host of problems involves similar coupling
requirements, e.g. the molecular rotation may couple with the electron’s orbital an-
gular momentum and its spin. And even in optical transitions between spin-orbit
coupled atomic states the photon adds an extra angular momentum from which the
optical selection rules are derived.
Generally, in order to determine the states of three angular momenta one starts
with the product states
|j1 m1 |j2 m2 |j3 m3 = |j1 m1 j2 m2 j3 m3
in an uncoupled representation. Formally, the total angular momentum vector oper-

ator is given by
J1 +
J = J2 +
J 3,
and one has to find eigenstates of J and Jz with the eigenvalues J (J + 1)2
2
and M. This may be done in two alternative schemes, based on the coupling of
two angular momenta described in Appendix B.2. One may first couple J 1 and
J2
to
J 12 and then combine J 12 with
J 3 to
J . According to (B.31) from the product
states |j1 m1 |j2 m2 one obtains
B.3 RACAH Function and 6j Symbols 569

(j1 j2 )J12 M12 = |j1 m1 |j2 m2
j1 m1 j2 m2 |J12 M12 ,
m1 m2
from which with |j3 m3

(j1 j2 )J12 j3 ; J M = (j1 j2 )J12 M12 |j3 m3
J12 M12 j3 m3 |J M (B.59)
M12 m3
follows. This state is simultaneously eigenstate of J , Jz and

2
J 12 with J12 being an
additional quantum number of the system. Alternatively one couples first J 2 with

J 3 to give J 23 and combines then J 23 with J 1 to
J . The eigenstate for the total
angular momentum J and its z-component Jz is then
2

j1 (j2 j3 )J23 ; J M = |j1 m1 (j2 j3 )J23 M23
j1 m1 J23 M23 |J M. (B.60)
m1 M23
This state is also eigenstate of

2
J 23 , and in this case J23 is an additional quantum
number. These two representations are of course not linearly independent from each
other – they describe the same subspace of angular momentum states. Thus, one
may express each state in one of the two coupling schemes by a linear combination
of the states in the other scheme:

(j1 j2 )J12 j3 ; J M (B.61)

= j1 (j2 j3 )J23 ; J M j1 (j2 j3 )J23 ; J M (j1 j2 )J12 j3 ; J M .
J23
The expansion coefficients are scalar quantities and independent of M. To write

them in a symmetric manner one uses the so called W -function after R ACAH (1942)
or the 6j symbol:

j1 (j2 j3 )J23 ; J M (j1 j2 )J12 j3 ; J M (B.62)
= (2J12 + 1)1/2 (2J23 + 1)1/2 W (j1 j2 Jj3 ; J12 J23 )

−j1 −j2 −j3 −J j1 j2 J12
with W (j1 j2 Jj3 ; J12 J23 ) = (−1) . (B.63)
j3 J J23
B.3.2 Orthogonality and Symmetries
For the 6j symbols not to disappear, the 6 angular momenta must be coupled accord-
ing to the above definitions. This requires triangular relations between the angular
momenta. Schematically the following triangular relations must be satisfied:

, , , . (B.64)

The 6j symbols are invariant against exchanging any two columns or any two rows:

j1 j2 J12 j1 J12 j2 j2 J12 j1 J J23 j1
= = = , etc.
j3 J J23 j3 J23 J J J23 j3 j2 J12 j3
(B.65)
Finally, a number of sum rules hold for the 6j symbols. We note

j1 j2 k
(−1) (2k + 1)
2k
= 1, (B.66)
j2 j 1 J
k
and the orthogonality relation

j1 j2 J j1 j2 J
(2J + 1) 2J + 1 = δJ J . (B.67)
j3 j4 J j3 j4 J
J
B.3.3 General Formulae
One may develop explicit expressions for the 6j symbols from (B.59)–(B.61). One
finds according to R ACAH:

j1 j2 J12
(B.68)
j3 J J23
(−1)t (t + 1)!
= (j1 j2 J12 )(j1 J J23 )(j3 j2 J23 )(j3 J J12 )
t
f (t)
with f (t) = (t − j1 − j2 − J12 )!(t − j1 − J − J23 )!(t − j3 − j2 − J23 )!

× (t − j3 − J − J12 )!(j1 + j2 + j3 + J − t)!
× (j2 + J12 + J + J23 − t)!(J12 + j1 + J23 + j3 − t)!
and the triangular function (abc) according to (B.47). The summation is again
over all nonvanishing terms. Again it is commendable to use one of the available
Java-applets for practical evaluations.
The 6j symbols may also be expanded as sums over products of 3j symbols. An
important relation is the contraction formula:

j1 +j2 +j3 +μ1 +μ2 +μ3 1 j2 j3
(−1)
m1 μ2 −μ3
μ1 μ2 μ3

j1 2 j3 j1 j2 3
×
−μ1 m2 μ3 μ1 −μ2 m3

1 2 3 1 2 3
= . (B.69)
m1 m2 m3 j1 j2 j3
B.4 Four Angular Momenta and 9j Symbols 571
For the special case that 1 + 2 + 3 is even and j3 = 1/2, a particularly simple
relation emerges:

j1 j2 3
= −(−1)−1 −2 −j2 −j1 (21 + 1)(22 + 1) (B.70)
−1/2 1/2 0

1 2 3 1 2 3
× .
j2 j1 1/2 0 0 0
B.3.4 Special Cases
Again, some closed expressions for special cases are occasionally useful. With s =
a + b + c and X = b(b + 1) + c(c + 1) − a(a + 1):

a b c (−1)s δ(abc)δbe δcd
=√ (B.71)
0 d e (2b + 1)(2c + 1)

a b c 2(−1)s+1 X
=√ (B.72)
1 c b 2b(2b + 1)(2b + 2)2c(2c + 1)(2c + 2)

a b c 2(−1)s
=√ (B.73)
2 c b (2b − 1)2b(2b + 1)(2b + 2)(2b + 3)
[3X(X − 1) − 4b(b + 1)c(c + 1)]
×√
(2c − 1)2c(2c + 1)(2c + 2)(2c + 3)

a+ 1
a 1
(−1)s+1 (s − 2c + 1)(2 + s)
2 2 = (B.74)
b+ 1
2 b c + 12 2 (2a + 1)(a + 1)(2b + 1)(b + 1)

a+ 1
2 a 1
2 = (−1) s+1 (s − 2c + 1)(2 + s)
. (B.75)
b b+ 2 c
1 2 (2a + 1)(a + 1)(2b + 1)(b + 1)
B.4 Four Angular Momenta and 9j Symbols
Very briefly, we mention the coupling of four angular momenta, j1 , j2 , j3 and

j4 , which again may be accomplished in different sequences. E.g. one may cou-
ple |(j1 j2 )j12 , (j3 j4 )j34 ; j m or alternatively |(j1 j3 )j13 , (j2 j4 )j24 ; j m. The two
schemes relate to each other by a unitary transformation:

(j1 j3 )j13 , (j2 j4 )j24 ; j m (B.76)

= (j1 j2 )j12 , (j3 j4 )j34 ; j m (j1 j2 )j12 , (j3 j4 )j34 ; j (j1 j3 )j13 , (j2 j4 )j24 ; j .
j12 ,j34
As a short notation for the recoupling coefficients

(j1 j2 )j12 , (j3 j4 )j34 ; j (j1 j3 )j13 , (j2 j4 )j24 ; j (B.77)
⎧ ⎫

1/2 ⎨ j1 j2 j12 ⎬
= (2j12 + 1)(2j34 + 1)(2j13 + 1)(2j24 + 1) j3 j4 j34
⎩ ⎭
j13 j24 j
the so called W IGNER 9j symbols are used {given in curly brackets}.

Each column and each row has to satisfy a triangular relation, and an odd number

of permutations of rows or columns only changes the sign according to (−1) all j ’s .
The orthonormality relation reads

(2j12 + 1)(2j34 + 1)(2j13 + 1)(2j24 + 1)
j13 ,j24
⎧ ⎫⎧ ⎫
⎨ j1 j2 j12 ⎬ ⎨ j1 j2 j12 ⎬
× j3 j4 j34 j3 j4 j34 = δj13 j δj24 ,j .
⎩ ⎭⎩ ⎭ 13 24
j13 j24 j j13 j24 j
For later use, we also communicate here one useful formula. In the case that one of
the j ’s is zero, the 9j symbol reduces to a 6j symbol:
⎧ ⎫
⎨a b c ⎬
δcf δgh (−1)b+d+c+g a b c
d e f = . (B.78)
⎩ ⎭ [(2c + 1)(2g + 1)]1/2 e d g
g h 0
c.c.: ‘complex conjugate’.

HFS: ‘Hyperfine structure’, splitting of atomic and molecular energy levels due to
interactions of the active electron with the atomic nucleus (Chap. 9).
References
B LUM, K.: 2012. Density Matrix Theory and Applications. Atomic, Optical, and Plasma Physics,
vol. 64. Berlin, Heidelberg: Springer Verlag, 3rd edn., 343 pages.
B RINK, D. M. and G. R. S ATCHLER: 1994. Angular Momentum. Oxford: Oxford University Press,
3rd edn., 182 pages.
C ONDON, E. U. and G. S HORTLEY: 1951. The Theory of Atomic Spectra. Cambridge, England:
Cambridge University Press, 441 pages.
E DMONDS, A. R.: 1996. Angular Momentum in Quantum Mechanics. Princeton, NJ, USA: Prince-
ton University Press, 154 pages.
R ACAH, G.: 1942. ‘Theory of complex spectra II’. Phys. Rev., 62, 438–462.
S VEN G ATO R EDSUN: 2004. ‘3j 6j 9j -symbol java calculator’, Sven Gato Redsun. http://www.
svengato.com/, accessed: 8 Jan 2014.
References 573
W EISSBLUTH, M.: 1978. Atoms and Molecules. Student Edition. New York, London, Toronto,
Sydney, San Francisco: Academic Press, 713 pages.
W EISSTEIN, E. W.: 2004a. ‘Wigner 3j -symbol’, Wolfram Research, Inc., Champaign, IL, USA.
http://mathworld.wolfram.com/Wigner3j-Symbol.html, accessed: 8 Jan 2014.
W EISSTEIN, E. W.: 2004b. ‘Wigner 6j -symbol’, Wolfram Research, Inc., Champaign, IL, USA.
http://mathworld.wolfram.com/Wigner6j-Symbol.html, accessed: 8 Jan 2014.
Matrix Elements
C
In this appendix some tools are collected which are useful for evaluating matrix ele-
ments of irreducible tensor operators. These matrix elements are needed to compute
transition probabilities for optical excitation of atomic and molecular states as well
as for the analysis of collision induced processes.
C.1 Tensor Operators
C.1.1 Definition
According to R ACAH (1942) one defines as irreducible tensor operator Tk of the

rank k each operator whose 2k + 1 components Tkq (q = −k, −k + 1, . . . , k) sat-
isfy the same commutation rule in respect of
J as the spherical harmonic operators
Ykq (θ, ϕ). Following R ACAH this implies in our notation (B.3)1 for the spherical
components of the angular momentum operator J:
[Jz , Tkq ] = q Tkq and (C.1)

1
[J± , Tkq ] = ∓ (k ∓ q)(k ± q + 1)Tkq±1 . (C.2)
2
B RINK and S ATCHLER (1994) define – equivalently – a spherical tensor (operator)
Tk of rank k as a quantity defined by 2k + 1 components, which transforms upon co-
ordinate rotation in the same way as the irreducible representation Dk of the rotation
group (see Appendix E):

Tkq

= Tks Dksq (αβγ ). (C.3)
s
1 We refer to J± = ∓ √1 (Jx ± iJy ) while R ACAH gives the relation for ∓(Jx ± iJy ). See also
2
footnote 1 in Appendix B.

576 C Matrix Elements
Here Tkq is the component of the tensor in the new coordinate system which arises
by rotating the old, un-dashed system through the E ULER angles αβγ . It is rep-
resented in term of the components Tks of the tensor in the old system. Important
examples of tensor operators are the spherical harmonics Ym (θ ϕ) (rank ) them-
selves, or somewhat more general the eigenstates |j m of the angular momentum
operator (rank j ).
The adjoint (or Hermitian conjugate) operator Tkq †
of a tensor operator Tkq is
defined by (see Sect. 2.3.1)
† † ∗
J M Tkq |J M = Tkq J M J M =
J M|Tkq JM , (C.4)
and with the C ONDON and S HORTLEY (1951) phase convention
Tkq
†
= (−1)q Tk−q . (C.5)
If Tkq is simply a complex function this is equivalent to Tkq †

= Tkq
∗ , as e.g. in the
case of the spherical harmonics (B.26).

A tensor is called Hermitian or self adjoint if Tkq
†
= Tkq . Obviously, with (C.4)
the diagonal matrix elements (and hence the eigenvalues) are then real: Hermitian
operators describe measurable, real quantities.
Tensors of rank 1 are called vector operators, e.g. the position vector r, the unit
vector of polarization e, the dipole moment D, as well as all angular momentum
operators, such as S,
L,
J, . The components of a vector operator V
I or F in the
spherical basis are
±1 = ∓ √1 [V
V y ];
x ± iV 0 = V
V z . (C.6)
2
C.1.2 WIGNER-ECKART Theorem
When evaluating matrix elements for a tensor operator, the W IGNER -E CKART theo-
rem is very useful. It says, that for any irreducible tensor operators of a given rank k,
the matrix elements between states |J M and |J M depend in identical form on
the projection quantum numbers M, M , and q:

γ J M Tkq |γ J M
#
= J Mkq J M γ J #Tk γ J (C.7)

√ J J k #
= (−1)J −k+M 2J + 1 γ J #Tk γ J (C.8)
−M M q

J −M
√ J k J #
= (−1)
2J + 1 γ J #Tk γ J . (C.9)
−M q M
C.1 Tensor Operators 577
The thus defined reduced matrix element2

γ J Tk γ J is independent of M , M
and q. Due to the properties of the 3j symbol the matrix elements are non-zero only
if M = M − q and if the triangular relation δ(J kJ ) = 1 holds!
In practice, to determine the reduced matrix element one has to evaluate just
one nonvanishing matrix element (preferably a particularly simple one) and to di-
vide it by the corresponding C LEBSCH -G ORDAN coefficient, e.g.
J Tk J =
J 0|Tk0 |J 0/
J 0|J k00 if J + J + k is even.
An important example is the reduced matrix element of an angular momentum.
With

J M Jz |J M = δJ J δM M M (C.10)

√ J 1 J #
= (−1)J −M 2J + 1 J #
J J
−M 0 M
and (B.55) for the 3j symbol, one obtains:

#
J #J J = δJ J J (J + 1). (C.11)
The W IGNER -E CKART theorem allows one to relate two matrix elements of dif-
ferent tensor operators, Sk and Tk of the same rank k with each other in a simple
manner. The ratio R of the reduced matrix elements of two tensor operators of the
same rank k may be computed from any pair of (nonvanishing) matrix elements of
their components:

γ J Tk γ J
γ J M |Tkq |γ J M
R J , J, T, S = = . (C.12)

γ J Sk γ J
γ J M | Skq |γ J M
Specifically for vector operators V with (C.7) we write

γ J M V q |γ J M = R γ J M J q |γ J M, (C.13)
which is independent of M and M and holds for all components V q .

The diagonal matrix elements of the scalar product V · J may be written

γ J M|V·J |γ J M =
γ J M|V γ J M · γ J M J |γ J M, (C.14)
M
where we have simply inserted the quantum mechanical unit operator

1 = M |γ J M
γ J M |. With (C.13), this expression becomes
Our definition of reduced matrix elements follows B RINK and S ATCHLER (1994), as-
suming, however, integer rank only, so that (−1)2k = 1. √ Note that these reduced
matrix elements are not symmetric in J and J , rather (2J + 1)
γ J T γ J =
√ k
(2J + 1)
γ J Tk γ J . R ACAH √ (1942), E DMONDS (1996) and others use a symmetric
definition:
γ J Tk γ J Racah = 2J + 1
γ J Tk γ J .

·

γ J M|V J |γ J M = R J γ J M γ J M

γ J M| J |γ J M (C.15)
M
= R
γ J M|
2
J |γ J M = RJ (J + 1)2 .
In the second line the eigenvalue (B.12) of

2
J has been used, so that finally

γ J M|V·J |γ J M
R= . (C.16)
J (J + 1)2
Inserting this back into (C.13) gives the very useful projection theorem

γ J M|V·J |γ J M
γ J M Vq |γ J M = γ J M Jq |γ J M. (C.17)
J (J + 1) 2
√ realizes that (V · J )J /J (J + 1) is the projection of V onto the unit vector

If one 2
J / J (J + 1), its physical relevance becomes evident. The projection theorem is

used e.g. in a coupled scheme of angular momenta, to express the matrix elements
of individual components in terms of the total angular momentum J. Specifically
z one obtains with
γ J M |Jz |γ J M = MδM M
for q = 0 =

γ J M|V·J |γ J M
z |γ J M =

γ J M|V M. (C.18)
J (J + 1)
C.2 Products of Tensor Operators

Direct products of matrices are an important concept in matrix algebra (see e.g.
B LUM, 2012, Appendix A). If A is N dimensional and B is n dimensional, then the
direct product A ⊗ B is N n dimensional.
Similarly, from tensor operators Rk1 and Uk2 of rank k1 and k2 , respectively, one
may construct (2k1 + 1)(2k2 + 1) components of new tensor operators. These can
be expressed in irreducible form again as direct product Rk2 ⊗ Uk2 by tensors TK of
rank K with |k1 − k2 | ≤ K ≤ |k1 + k2 |:

TKQ = [Rk2 ⊗ Uk2 ]KQ = k1 q1 U
R k2 q2
k1 q1 k2 q2 |KQ
q1 q2
(C.19)
= k1 q U
R k2 Q−q
k1 qk2 Q − q|KQ.
q
Here
k1 k2 q1 q2 |KQ is a C LEBSCH -G ORDAN coefficient as introduced by (B.31)
in the context of angular momentum coupling.
Specifically, with (B.36) and (B.48) the scalar product (rank K = 0) of two ten-
sor operators of the same rank k becomes simply

Rk · Uk = kq U
(−1)q R k−q . (C.20)
C.2 Products of Tensor Operators 579
This is the generalization of the standard scalar product of two vectors R and S (see
e.g. (B.8)). The result is a single scalar quantity.
C.2.1 Products of Spherical Harmonics
Application of√the relations given above to the renormalized spherical harmonics

(B.29), Ckq = 4π/(2k + 1)Ykq , leads to a number of useful expansion formulae.
(1) (1)
With (C.20) the scalar product of the two tensor operators C = C (θ1 , ϕ1 ) and
(2) (2)
C = C (θ2 , ϕ2 ) at different angles becomes:
(1) (2)

C · C = (−1)m Cm (θ1 , ϕ1 )C−m (θ2 , ϕ2 ). (C.21)
m=−
If the coordinate system is such that θ2 ϕ2 defines the z-axis, we have C−m (θ2 , ϕ2 ) =
δm0 , and the sum reduces to C0 (γ 0) = P (cos γ ), with γ being the angle between
the two direction in space characterized by (θ1 , ϕ1 ) and (θ2 , ϕ2 ). Rewriting
∗
(−1)m C−m = Cm
we obtain the addition theorem for the renormalized spherical harmonics:

∗
P (cos γ ) = Cm (θ1 , ϕ1 )Cm (θ2 , ϕ2 ) (C.22)
m=−

= Cmp (θ1 , ϕ1 )Cmp (θ2 , ϕ2 ). (C.23)
m=0,p=±1
The second line is easily verified with the definition of real tensor operators (D.5)
applied to the (renormalized) real spherical harmonics Cmp (θ, ϕ) (D.7). One also
derives from (C.19) a useful expansion formula for the product of two spherical
harmonics at the same angle

kq m m C m (θ, ϕ)Cm (θ, ϕ) = k0 00 Ckq (θ, ϕ), (C.24)
m m
where the normalization constant

k0| 00 has been derived from the definition of
spherical harmonics at θ = ϕ = 0. Using the orthogonality relations (B.38) for the
C LEBSCH -G ORDAN coefficients one also obtains the inversion of this relation:

C∗ m (θ, ϕ)Cm (θ, ϕ) = Ckq (θ, ϕ) kq m m k0 00 . (C.25)
kq
C.2.2 Matrix Elements of the Spherical Harmonics
The often used matrix elements of the spherical harmonics in an |m basis, nor-
malized as
√
(2 + 1)(2 + 1)
m Ckq |m = C∗ m (θ, ϕ)Ckq (θ, ϕ)Cm (θ, ϕ)dΩ,
4π
(C.26)
may be evaluated by replacing the latter two functions with the expansion (C.25):
√

(2 + 1)(2 + 1)
m Ckq |m =
4π

× C∗ m (θ, ϕ)Ck q (θ, ϕ)dΩ k q kqm k 0 k00
k q

2 + 1
=
δk δq m k q kqm k 0 k00 .
2 + 1
kq
Thus, we finally obtain:

2 + 1

m Ckq |m =
kqm m k00 0 (C.27)
2 + 1

m Ckq |m = (−1)m 2 + 1 (2 + 1) × δm m+q δ k (C.28)

k k
×
0 0 0 −m q m

−m
√ k #

m Ckq |m = (−1)
2 + 1 #Ck . (C.29)
−m q m
The last equation is simply the W IGNER -E CKART theorem for the matrix element.
Comparing the latter two equalities gives the reduced matrix element of Ck :

# k
#
Ck = (−1) (2 + 1) . (C.30)
0 0 0
We recall that this expression is zero if + k + is odd. We also note that

√
# #
− (2 + 1) #
#

Ck = (−1) √ Ck . (C.31)
(2 + 1)
For k = 0 this implies

#
#C0 = δ , (C.32)
C.2 Products of Tensor Operators 581
and more generally for = one obtains with (B.50)

(−1)k/2 k!( + k/2)! (2 + 1)(2 − k)!

Ck = . (C.33)
(k/2)!2 ( − k/2)! (2 + k + 1)!
Note that this expression only holds for even k. The reduced matrix element vanishes
for odd k. For the special case C2 one obtains:
√
( + 1)

C2 = − √ . (C.34)
(2 − 1)(2 + 3)
Note the minus sign!
Of special importance in respect of the selection rules for electric dipole transi-
tions is according to (4.79) the case k = 1. Because of (B.34) and (B.49)
parity conservation holds: = ± 1 (C.35)
(see also Appendix D). With (B.50) the only nonvanishing matrix elements are
⎧
# ⎨ +1
for = + 1
#C1 =
2+3
(C.36)
⎩−
(2−1) for = − 1,

and because of (B.43)–(B.2.3)

m C1q |m = (−1)q
−m|C1q −m (C.37)

= −m C1−q | −m = (−1)q
m|C1−q m .
Hence, in dipole transitions the selection rule for the projection quantum number
becomes m = q. The matrix elements vanish unless m = m ± 1 or m = m. A de-
tailed evaluation of (C.29), using (B.52)–(B.55) leads to:

( − m + 1)( + m + 1)
( + 1)m C10 |m = (C.38)
(2 + 1)(2 + 3)

( + m + 1)( + m + 2)
( + 1)(m + 1) C11 |m = (C.39)
2(2 + 1)(2 + 3)

( − m + 1)( − m + 2)
( + 1)(m − 1) C1−1 |m = (C.40)
2(2 + 1)(2 + 3)

( − m)( + m)
( − 1)m C10 |m = (C.41)
(2 − 1)(2 + 1)

( − 1 − m)( − m)
( − 1)(m + 1) C11 |m = − (C.42)
2(2 − 1)(2 + 1)

( − 1 + m)( + m)
( − 1)(m − 1) C1−1 |m = − . (C.43)
2(2 − 1)(2 + 1)
For the particularly simple case of s ↔ p transitions one finds that all allowed tran-
sitions have the same amplitudes:

10|C10 |00 =
00|C10 |10 =
11|C11 |00 (C.44)

=
1 −1|C1−1 |00 =
00|C11 |1 −1 =
00|C1−1 |11 = 1/3.
C.3 Reduction of Matrix Elements
Often matrix elements of tensor operators TKQ have to be evaluated in a scheme

of coupled angular momenta, such as |(LS)J M. Typically, these operators may be
composed according to (C.19) from two tensor operators, R k1 q1 (1) which acts only

on the first component of the eigenstate, and Uk2 q2 (2) which acts only on the second
component.
With the W IGNER -E CKART theorem (C.9), the matrix element of TKQ between
state |γ LSJ M and |γ L SJ M is:

L S J M TKQ |LSJ M

J −K+M
√ J J K #
= (−1)
2J + 1 L S J #TK LSJ . (C.45)
−M M Q
For evaluating the reduced matrix elements of product tensors angular momentum
algebra provides a useful toolbox. In simple cases, with some algebra and exploiting
6j symbols (B.61), the reduced matrix elements in the coupled scheme |(LS)J M
may be recast into the uncoupled scheme |LML |SMS . We communicate here only
(1)
some results. If Rk acts only on the first angular momentum of the coupled scheme
(2)
and Uk ≡ 1, we have:
# (1)

L S J #Rk LSJ = δS S (−1)k+L +S+J (2J + 1) 2L + 1

L L k #
× L #Rk L. (C.46)
J J S
Conversely, if Rk ≡
(1)
1 and U acts only onto the second angular momentum in
the coupled scheme, we obtain:
# (2)

L S J #Uk LSJ = δL L (−1)k+L+S+J (2J + 1) 2S + 1

S S k #
× S #Uk S. (C.47)
J J L
C.3 Reduction of Matrix Elements 583
Note: due to the well defined phases of the C LEBSCH -G ORDAN coefficients the se-
quence of the angular momenta is not arbitrary. For the scalar product (rank K = 0)
of two tensor operators of rank k the reduction becomes particularly clear. We first
notice that according to (C.7)
#
j1 j2 J M (Rk · Sk )00 |j1 j2 J M = δM M δJ J j1 j2 J #Rk · Sk j1 j2 J , (C.48)
where we have used the explicit expression (B.48) for the 3j symbol. Explicitly
(C.48) may be evaluated by inserting on the left side into the scalar product Rk · Sk
the quantum mechanical unit operator. Then each part may be reduced according
to (C.46). By applying the orthogonality relations according to R ACAH (1942) (if
one has only to average over the angular momentum part) one finds for the reduced
matrix element of the scalar product:
#
j1 j2 J #Rk · Sk j1 j2 J = 2j1 + 1) 2j2 + 1 (C.49)

j j k # #
× (−1)J +j1 +j2 1 1 j1 #Rk j1 · j2 #Sk j2 .
j2 j 2 J
A somewhat different situation is encountered when a tensor TK is the product of

two tensor operators Rk1 and Sk2 which are constructed from the same coordinates,
momenta etc., and thus act on the same system. From simple angular momentum
recoupling, E DMONDS (1996) obtains in this case (Eq. (7.1.1)):
# √
j #(Rk1 Sk2 )K j = 2K + 1(−1)K+j +j (C.50)
k1 k2 K #
× j #Rk j¯
j¯Sk j .
j j j¯
j¯
C.3.1 Matrix Elements of the Spherical Harmonics in LS Coupling
Most often required√ are the matrix elements of the spherical harmonics Yk (or of the
renormalized Ck = 4π/(2k + 1)Yk ). We have described these in Appendix C.2.2
already in a basis of pure n states. For LS coupled orbital angular momenta with
orbital quantum numbers and the reduced matrix elements
Ck are given
by (C.28).3 In the coupled scheme with a total electron spin S the reduced matrix
element (C.46) is:
3 The following expressions are also valid in multi-electron systems as long as there is only one
active electron (while further electrons have zero orbital angular momentum as it is the case for
alkali atoms, or for He below the first ionization limit). Here and is identical to the total orbital
angular momenta L and L, respectively, while the total spin S ≥ 1/2 of the system can in principle
be composed from several particles.
#
S J #Ck SJ = δS S (2J + 1) 2 + 1 (2 + 1) (C.51)

k k
× (−1)−S− −−J .
J J S 0 0 0
In this case, inverting the reduced matrix element leads to

√
#
J −J (2J + 1)
#
#

SJ Ck SJ = (−1) √ SJ #Ck SJ . (C.52)
(2J + 1)
This expression is only non-zero if + + k is even. Thus, (C.45) reads now

S J M Ckq |SJ M

= δS S 2J + 1 (2J + 1) 2 + 1 (2 + 1) (C.53)

J J k k k
× (−1)M −S .
−M M q J J S 0 0 0
Special Case: Spin 1/2
For the case S = s = 1/2 (e.g. for an effective one particle system with spin 1/2 –
i.e. electron in an atom or a single active proton in a nucleus), using (B.70) reduces
(C.51) to:
$ # # %
# #
1 # # 1 j −1/2+k
j j k
j #Ck # j = (−1) (2j + 1) × . (C.54)
2 2 1/2 −1/2 0
This expression is even independent of and (of course + + k must be even)

and one obtains for (C.53):
$ %

1
1
j m Ckq j m = (−1)j −m +j −1/2+k 2j + 1 (2j + 1)
2 2

j j k j j k
× . (C.55)
m −m q 1/2 −1/2 0
For the evaluation of line strengths in E1 transitions, we report here some values for
the reduced matrix element of C1 in the case of a one electron systems:
j j
# # 1/2 3/2 5/2
$ % √ √
# # 1
1 # 1/2 − 1/3
j #C1 #
1/3 0
2 # 2 :
j √
3/2 − 1/3
√
− 1/15
√
2/5
(C.56)
√ √
5/2 0 − 2/5 − 1/35
C.3 Reduction of Matrix Elements 585
C.3.2 Scalar Products of Angular Momentum Operators
Scalar products of coupled angular momenta are most conveniently evaluated by

using binomial formulas. We exemplify this for the product of angular momentum
L and spin
S which is the crucial operator in spin-orbit interaction. As discussed in
L ·
Chap. 6, the operator S commutes with the square J and the projection Jz of the
2
total angular momentum J = L+S. In the scheme of coupled angular momenta, i.e.
when the system is described by eigenstates |LSJ MJ , the good quantum numbers
are L, S, J and MJ . From the first binomial formula one obtains:

LSJ MJ L ·
S|LSJ MJ
1 2
LSJ MJ
J −L −
2 2
= S |LSJ MJ
2
2
= J (J + 1) − L(L + 1) − S(S + 1) δJ J δMJ MJ . (C.57)

2
However, one often needs to express the matrix elements in the uncoupled basis of
eigenstates |LML SMS , e.g. in the case of strong magnetic fields as described in
Sect. 8.1.3. Thus, for uncoupled L and
S one returns to the definition of the scalar
product according to (B.8)

LML SMS L ·S|LML SMS

= − LML SMS L+
S− |LML SMS (C.58)

− LML SMS S+ |LML SMS + LML SMS
L− Lz
Sz |LML SMS ,
and uses the matrix elements (B.14)–(B.17) for the angular momenta. Since the
q act only onto the LML component of the state vector and
operators L Sq only onto
the SMS component one sees that the matrix elements are only nonvanishing for
MJ = ML + MS = ML + MS = MJ . (C.59)
Hence, MJ = ML + MS is a good quantum number, albeit J is not. Three types of

nonzero matrix elements exist in the uncoupled system:

L(ML + 1)S(MS − 1) L ·
S|LML SMS

= L(ML + 1)S(MS − 1) L+
S− |LML SMS

= 2 L(L + 1) − ML (ML + 1) S(S + 1) − MS (MS − 1) /4 (C.60)

L(ML − 1)S(MS + 1) L ·
S|LML SMS
−
= −
LS ML − 1 MS + 1|L S+ |LML SMS

= 2 L(L + 1) − ML (ML − 1) S(S + 1) − MS (MS + 1) /4 (C.61)

L ·
Table C.1 Matrix elements of S/2 for a 2 P state in the uncoupled basis |LML SMS , with
υ = ML + 2MS .
ML MS |1 12 |0 12 |1 − 12 |−1 12 |0 − 12 |−1 − 12
υ 2 1 0 0 −1 −2
MJ 3/2 1/2 1/2 −1/2 −1/2 −3/2
1 12 | 1/2 0 0 0 0 0
√
0 12 | 0 0 1/ 2 0 0 0
√
1 − 12 | 0 1/ 2 −1/2 0 0 0
√
−1 12 | 0 0 0 −1/2 1/ 2 0
√
0 − 12 | 0 0 0 1/ 2 0 0
−1 − 12 | 0 0 0 0 0 1/2
L ·

LML SMS | S|LML SMS
z
= −
LML SMS |L Sz |LML SMS = 2 ML MS . (C.62)
Table C.1 provides as an example all LS matrix elements for a 2 P state (L = 1,

S = 1/2).
C.3.3 Components of Angular Momenta
As a further example we compute the z-component of an angular momentum which

acts only on one part of the coupled system. Typical applications are the components
Sz or Lz in a spin-orbit coupled scheme |(SL)J MJ , or Iz and Jz in the hyperfine
coupled scheme |(I J )F MF . We use here the latter quantum numbers, which for
other application just have to be replaced appropriately.
We first derive the reduced matrix element of J according to (C.46):
#
I J F #J I J F (C.63)

J J 1 #
= (−1)1+I +J +F δI I (2F + 1) 2J + 1 J #J J
F F I

J J 1
= (−1)1+I +J +F δI I δJ J (2F + 1)J (J + 1) 2J + 1 ,
F F I
where in the last step (C.11) was used. The nonvanishing matrix elements of the
components of J may now be written with the W IGNER -E CKART theorem (C.7),
e.g.

J I F MF Jz |J I F MF (C.64)

√ F F 1 #
= (−1)F −1+MF δMF MF 2F + 1 J I F #J J I F .
−MF MF 0
Inserting (C.63) yields:

C.4 Electromagnetically Induced Transitions 587

J I F MF Jz |J I F MF
= (−1)2F +MF +I +J δMF MF (C.65)

F F 1 J J 1
× 2F + 1 (2F + 1)(2J + 1)(J + 1)J .
−MF MF 0 F F I
Thus, these matrix elements are diagonal in MF , I and J . We may finally insert the
explicit expressions of the 3j symbols from (B.55) and (B.54). We have to distin-
guish two cases:
(a) F = F

J I F MF |Jz |J I F MF

√
3F +I +J MF (2F + 1)(2J + 1)(J + 1)J J J 1
= (−1) √
F (F + 1) F F I
(−1)2I +2J +1 F (F + 1) + J (J + 1) − I (I + 1)
= MF (C.66)
2 F (F + 1)
except for F = 0 where
J I F MF |Jz |J I F MF / = 0.
(b) F = F + 1

J I (F + 1)MF |Jz |J I F MF

J J 1
= (−1)3F +I +J +1
F F +1 I

2(F + MF + 1)(F − MF + 1)(2J + 1)(J + 1)J
×
(2F + 2)

(−1)4F +2I +2J +2 MF 2
= 1− (C.67)
2 F +1

(J + I − F )(F + J + I + 2)((F + 1)2 + (J − I )2 )
× .
(2F + 1)(2F + 3)
In the last step we also have inserted the explicit expression for the 6j symbols
(B.72) to obtain these useful, compact relations.
C.4 Electromagnetically Induced Transitions

Probably the most important application for the tools described here are transition
matrix elements for transitions induced by electromagnetic radiation. We shall dis-
cuss these for electric dipole (E1) and quadrupole (E2), as well as for magnetic
dipole (M1) transitions.
C.4.1 Electric Dipole Transitions
Let us begin with emission or absorption of a photon in an E1 transition. As

discussed in detail in Chap. 4, the probability of such a transition between state
|a = |γ J M and state |b = |γ J M is proportional to the absolute square of
matrix elements of the type
1 2
2 2

γ J M r · e|γ J M = γ r|γ J M C1q |J M · e∗q . (C.68)

q=−1
Since C1 may be seen as a tensor of rank 1, this expression contains in principle the
(2 × 1 + 1)(2 × 1 + 1) components of the product tensor. One may express these
in irreducible form by tensors of rank 0 (basically the total intensity), rank 1 (so
called orientation) and rank 2 (so called alignment). We shall come back to this in
Appendix C, Vol. 2.
For low Z atoms, LS coupling is characteristic according to the scheme
|γ LSJ M and |γ L S J M . In this case the selection rules are determined by
the matrix elements
S L J M |C1q |SLJ M. Equation (C.53) factors this matrix
element into its important components. In an electromagnetically induced transi-
tion, the total electron spin does not change, i.e. S = 0. For E1 transitions we have
k = 1 and with q = 0, ±1 one reads in (C.53) from the first 3j symbol the selection
rules for J and M: M = q and δ(J 1J ) = 1. Thus M = M ± 1 or M = M and
J = J ± 1 or J = J – however, 0 0 is strictly forbidden. Finally, the last 3j
symbol recovers the parity selection rule L = L ± 1.
C.4.2 Electric Quadrupole Transitions
According to (5.56) the crucial matrix element for E2 transitions is

1

a|T0 T|b(E2) ∝
b|Q2q+ |a = √
b|r 2 |a (−1)q
b|C2q |a +
b|C2−q |a
2
(C.69)
1
and ∝
b|Q2q− |a = √
b|r 2 |a (−1)q
b|C2q |a −
b|C2−q |a ,
2i
where the definitions (D.5) have been inserted. Since k = 2, we note that q = 0,
±1, or ±2. In LS coupling we use again (C.53) for evaluation. Again S = 0,
and considering the triangular rule δ(J J 2) = 1, we read from the 3j symbols that
the total angular momentum J may now change by 0, by ±1 or ±2 units of ,
now with the restriction 0 0 and 1/2 1/2. With M = q follows in this case,
that transitions are possible with M = M, as well as with M ± 1 and even with
M ±2. This leads to correspondingly structured quadrupole absorption and emission
patterns. In addition, for quadrupole transitions, parity conservation now implies
L = L ± 2.
C.4 Electromagnetically Induced Transitions 589
C.4.3 Magnetic Dipole Transitions
Selection rules for M1 transitions are derived from the matrix element (5.53)

a|eE0 L + 2
D|b(M1) ∝
b| J +
S|aB =
b| S|aB , (C.70)
where the index B indicates that the coordinate frame for orbital angular momentum
L and spin
S is chosen here with its z-axis parallel to the magnetic RF field inducing
the transition. This particular polarization dependence can be expressed again by the
W IGNER -E CKART theorem (C.9). Since we discuss a dipole transition with k = 1
we obtain:
√
L + 2

b| S|aB = γ γ (−1)J −1+M 2J + 1 (C.71)

J J 1 # #
× J # LJ + 2 J #
SJ .
−M M q
With
γ |γ we describe the overlap integral of radial part of the wave function
between initial and final state. The 3j symbol determines the selection rule for the
magnetic quantum numbers M, with q referring in this case to the direction of the
magnetic field vector (rather than the electric field in the E1 case). In spectroscopic
experiments, typically, radio frequency (RF) or microwave radiation (MW) is used
in external, static magnetic field B st , defining the z-axis. If the radiation field vector
B points into this z-direction (i.e. if the polarization vector e and the wave vector k
lie in the xy plane), then q = 0 and transitions with M = M occur. To induce M =
±1 transition (q = ±1), the B vector of the inducing field has to be perpendicular
to static field B st .
The two reduced matrix elements in (C.71) determine the selection rules for the
quantum numbers J , L and S. They have to be evaluated (for not too high static
magnetic fields) according to √(C.46) and (C.47) in the coupled√ system. With (C.11)
we have
L LL = δL L L(L + 1) and
S SS = δS S S(S + 1). Thus we
obtain
#

L S J # LLSJ = δS S δL L (−1)k+L +S +J (2J + 1) 2L + 1

L L 1
× L(L + 1) and (C.72)
J J S
#

L S J # SLSJ = δS S δL L (−1)k+L+S+J (2J + 1) 2S + 1

S S 1
× S(S + 1). (C.73)
J J L
Hence, the total spin and the total orbital angular momentum do not change during
a M1 transition in LS coupling! In contrast, transitions with J = J ± 1 or J = J
are possible, provided 0 0. We recall that the radial wave functions for different
principal quantum numbers and otherwise identical configuration are orthogonal.
Hence, only within one electronic state

γ |γ = 0, so that M1 transitions do not
occur between different electronic states. Of course, this strictly holds only for pure
LS coupling. In the case of configuration mixing or jj coupling one has examine
the situation in detail. We finally note, that all above considerations may be applied,
mutatis mutandis, to a hyperfine coupled scheme as well – typically prior to evalu-
ating the LS coupling.
C.5 Radial Matrix Elements
To obtain quantitative values for transition probabilities it is necessary to also com-

pute the radial parts of the matrix elements, as indicated by
γ . . . |Tkq |γ . . . above.
In general, the radial part may completely be pulled out of the matrix element, and
can be computed independently. For single electron wave functions the radial matrix
elements are
∞

γ r|γ = r 3 drRn (r)Rn (r). (C.74)
0
They are needed when evaluating probabilities for E1 transitions as described in

Chap. 4 but also for a quantitative description of the S TARK effect discussed in
Chap. 8. The radial eigenfunctions have to be known and these depend on – even
though the orbital angular momentum L has dropped out of the angular part of the
matrix element (C.54).
In closed form, these matrix elements may only be derived for the hydrogen atom
and H like ions. Using the known radial functions (2.122) one finds

4 (n − − 1)! (n − − 1)!
n r|n = 2 2 (C.75)
n n [(n + )!]3 [(n + )!]3
∞
+1 2+1 −ρ/2 −ρ /2 2
× Ln2 + ρ Ln+ (ρ)re e ρ ρ r dr,
0
with ρ = 2Zr/(na0 ) and ρ = 2Zr/(n a0 ) and the associated L AGUERRE polyno-

mials

n−−1
[(n + )!]2 ρk
L2+1
n+ (ρ) = (−1)k+1 .
(n − − 1 − k)!(2 + 1 + k)! k!
k=0
For not too large values of n and one may evaluate (C.75) in closed form,
using standard analytical programs like Maple, Mupad4 or Mathematica on a PC.
We assemble in Table C.2 some characteristic results for
n |r|n in (atomic,
Z scaled) units a0 /Z.
4 Available as part of the Symbolic Math Toolbox add-on for MATLAB.

C.5 Radial Matrix Elements 591
Table C.2 Radial transition n1 1 n2 2

n|r|n
matrix elements for the a0 /Z
hydrogen atom an H-like √
atoms 1 0 2 1 128 6/243 1.290
√
1 0 3 1 27 6/128 0.516
√
1 0 4 1 6144 15/78 125 0.305
√
1 0 5 1 250 30/6561 0.209
√
2 0 3 1 13 824 12/15 625 3.065
√
2 0 4 1 512 30/2187 1.282
√
2 0 5 1 576 000 60/5764 801 0.774
√
2 1 3 0 3456 18/15 625 0.938
√
2 1 3 2 27 648 180/78 125 4.748
If very high values for n and are required (RYDBERG atoms), there are suitable
alternatives. Typically, it is sufficient to compute
n , − 1|r|n, for n = n. Based
on earlier work a closed form has been given e.g. by T OWLE et al. (1996) (again in
units of a0 /Z):

(−)n − (n + − 1)!(n + )! 1/2
n , − 1 r|n, =
4Z (n − )!(n − − 1)!

(4n n)+1 (4n n)ν (n − n )N −ν−1 N !
× (C.76)
(n + n)n +n (2 − 1 + ν)!(N − ν)!
× 2 F1 (−ν, −2 + 1; N − ν + 1; x)

(−4n n)ν (n − n )N −ν −1 N !
−
(n + n )2 (2 − 1 + ν )!(N − ν )!

× 2 F1 −ν , −2 + 1 − ν ; N − ν + 1; x .
Here 2 F1 (α, β; γ ; x) is the hypergeometric series

(α)t (β)t
2 F1 (α, β; γ ; x) = xt (C.77)
t
(γ )t t!
with (α)t = α(α + 1) · · · (α + t − 1)

2
x = − n − n /4n n

ν = min n r , nr N = max n r , nr ,

ν = min n r , nr + 2 N = max n r , nr + 2 ,
and nr = n − and n r = n − − 1 are radial quantum numbers. The hypergeometric

series always terminates since α and β are negative numbers. Extended tables on
line strengths S(n sj − nsj ) or intensities (2j + 1)A(jj ) (with the E INSTEIN
coefficient A(jj ) corresponding to (4.114)) are found in T OWLE et al. (1996) for H
like RYDBERG atoms. Since for sufficiently high n and all atoms become hydrogen
like, these results are of general relevance.
E1: ‘Electric dipole’, transitions induced by the interaction of an electric dipole

with the electric field component of electromagnetic radiation.
E2: ‘Electric quadrupole’, transitions induced by the interaction of a quadrupolar
charge distribution with the electromagnetic radiation field.
good quantum number: ‘Quantum number for eigenvalues of such observables that
may be measured simultaneously with the H AMILTON operator (see Sect. 2.6.5)’.
M1: ‘Magnetic dipole’, transitions induced by the interaction of a magnetic dipole
with the magnetic field component of electromagnetic radiation.
MW: ‘Microwave’, range of the electromagnetic spectrum. In spectroscopy MW
usually refers to wavelengths from 1 mm to 1 m corresponding to frequencies be-
tween 0.3 GHz to 300 GHz; ISO 21348 (2007) defines it as the wavelength range
between 1 mm to 15 mm.
RF: ‘Radio frequency’, range of the electromagnetic spectrum. Technically, one
includes frequencies from 3 kHz up to 300 GHz or wavelengths from 100 km to
1 mm; ISO 21348 (2007) defines the RF wavelengths from 100 m to 0.1 mm; in
spectroscopy RF usually refers to 100 kHz up to some GHz.
References
E DMONDS, A. R.: 1996. Angular Momentum in Quantum Mechanics. Princeton, NJ, USA: Prince-
ton University Press, 154 pages.
ISO 21348: 2007. ‘Space environment (natural and artificial) – Process for determining solar
irradiances’. International Organization for Standardization, Geneva, Switzerland.
R ACAH, G.: 1942. ‘Theory of complex spectra II’. Phys. Rev., 62, 438–462.
T OWLE, J. P., P. A. F ELDMAN and J. K. G. WATSON: 1996. ‘A catalog of recombination lines
from 100 GHz to 10 microns’. Astrophys. J. Suppl. Ser., 107, 747–760.
Parity and Reflection Symmetry
D
The concept of parity conservation plays a key role in modern physics and is used
throughout this book. We present here a short introduction to parity and reflection
symmetry from an atomic and molecular physics perspective.
D.1 Parity
refers to spatial symmetry of states and is defined by:
The parity operator P

Pψ(r) = ψ(−r). (D.1)
We have described the central force problem in polar coordinates. With r → −r

they change as (r, θ, ϕ) → (r, π − θ, ϕ + π). As long as the interaction is spatially
isotropic (e.g. the C OULOMB potential) inversion has no influence on the Hamilto-
nian, hence P and H commute:
H
[P, ] = 0.
Thus, the eigenfunctions of the Hamiltonian are also eigenfunctions of the parity
operator. We distinguish states with positive and negative parity (alternatively also
has eigenvalues Pat = ±1:
called odd and even), i.e. P

Pψ(r) = ψ(−r) = ±ψ(r).
The product of two functions with unequal parity has negative parity, while the
product of two functions with the same parity has positive parity. We note that the
integral over all space disappears for a function F (odd) (r) with odd parity:
2π π
F (odd) (r)dΩ ≡ 0. (D.2)
0 0
For atomic orbitals we write explicitly

nm (r) = PR
Pψ n (r)Ym (θ, ϕ) = Rn (r)Ym (π − θ, ϕ + π).

594 D Parity and Reflection Symmetry
With the definition of the spherical harmonics (B.28) one finds
Ym (π − θ, ϕ + π) = (−1) Ym (θ, ϕ),
so that the parity of the states ψnm (r) is Pat = (−1) , hence, spherical harmonics
which differ by = ±1 have opposite parity.
Specifically, the relation
= −r
Pr (D.3)
holds, and we may say that the dipole operator D = −er has odd parity. As trivial
as that statement may seem, it has significant consequences in the context of selec-
tion rules for optical transitions. As discussed in detail in Chap. 4, for an optical
& 2π & π
transition to occur, the integral 0 0 Yb mb (θ, ϕ)rYa ma (θ, ϕ)dΩ must not disap-
pear. Thus, with (D.2) and (D.3) the product Yb mb (θ, ϕ)Ya ma (θ, ϕ) must have odd
parity and transitions are thus only allowed if the parity of initial |a ma and final
state |b mb is different. A dipole transition thus connects only states with opposite
parity. The selection rule for single electron transitions is = ±1.
Somewhat more general – expressing the particle point of view – the photon is
said to have odd parity, Pph = −1. The selection rule (4.86) for dipole transitions
may thus be inferred directly and elegantly from a general parity conservation rule
for the whole system – including atom and photon. Since the photon with its negative
parity disappears during absorption and appears in emission, absorption or emission
of a photon must be accompanied by a change of parity in the atomic system, hence
the selection rule = ±1.
D.2 Multi-electron Systems
The above discussion tacitly assumed a single electron, characterized by |m, ig-
noring its spin. The parity concept may, however, be extended naturally to multi-
electron systems, assuming that the spatial part of the total wave function |LM can
be written as a product of single electron functions (or as a linear combination of
products such as a Slater determinant). The total parity of an N electron system
is then the product of the parities of all its electron orbits. Thus, a configuration
{n1 1 n2 2 . . . nk k . . . nN N } has even or odd parity depending on whether
N
(−1) 1 i
= (−1)λ = ±1
is positive or negative, respectively (or alternatively whether λ = 0 or 1). In principle

one has to sum over all electrons of an atom; however, in practice it usually suffices
to sum just over all electrons in open shells.
D.3 Reflection Symmetry of Orbitals – Real and Complex Basis States 595
D.3 Reflection Symmetry of Orbitals – Real and Complex Basis

States
At this point some general remarks about the choice of basis states or wave functions
and their symmetry properties are in order. For simplicity we first discuss again a
single electron and ignore its spin.
To study different atomic problems some choices of basis states may be more
suitable than others. The one most commonly used in atomic physics for the angu-
lar part of the wave functions (states) is the representation by (complex) spherical
harmonics.
There are, however, a variety of cases where another symmetries may be more
adaptable to a given problem, such as the interaction with an external electric field
(see Sect. 8.2). In that case the eigenstates are linear combinations of states with
±M and |M| remains a good quantum number, while the sign of M is indefinite.
Similarly, in optical transitions the polarization of the exciting light may lead to
particular linear superpositions of different basis states as discussed in Chap. 4. All
these linear combinations are per definition also pure states, and in principle, one
can find an infinite number of such states which, properly orthonormalized, could
also serve as a basis set. In standard quantum mechanical textbooks the |m (or
|LM) states are somewhat overemphasized and one is led to believe that these are
the only suitable basis states for atomic systems. That is only true if a system is
characterized by the magnitude of angular momentum z .
2
L and its z-component L
In addition, the measurement to be described must select states which diagonalize
both operators simultaneously, so that
2
L |LM = L(L + 1)2 |LM
(D.4)
z |LM = M|LM.
L
And indeed, in the presence of a magnetic field in z-direction a typical atomic

Hamiltonian remains diagonal in this basis as discussed in Sects. 2.7 and 8.1. Such
properties of the complex angular momentum basis, together with the fact that the
corresponding matrices for coupling and rotating angular momenta are extensively
tabulated, makes them very attractive. The price to be paid is that linear combi-
nations have to be used already for rather simple applications, such as atoms in
external electric fields, dipole excitation by linearly polarized light, as well as for
most of molecular physics and chemistry.
Thus, one may construct real tensor operators Tkqp (observables, spherical har-
monics etc.) as linear combinations from the complex ones
with Tk−q = (−1)q Tkq

∗
for 0 < q ≤ k and p = ±1:
i(p−1)/2
i(p−1)/2
Tkqp = √ (−1)q Tkq + p Tk−q = √ (−1)q Tkq + p Tkq

∗
(D.5)
2 2
while for q = 0: Tk0+ = Tk0 and Tk0− = 0.
Table D.1 Renormalized real spherical harmonics Ckq for k = 1 to 3

k p = +1 p = −1
0 C00+ = 1 C00− = 0
1 C10+ = cos θ C10− = 0
1 C11+ = sin θ cos ϕ C11− = sin θ sin ϕ
2 C20+ = (3 cos2 θ − 1)/2 C20− = 0
√ √
2 C21+ = 3 sin θ cos θ cos ϕ C21− = 3 sin θ cos θ sin ϕ
√ √
2 C22+ = ( 3/2) sin2 θ cos 2ϕ C22− = ( 3/2) sin2 θ sin 2ϕ
3 C30+ = (5 cos3 θ − 3 cos θ)/2 C30− = 0
√ √
3 C31+ = ( 6/4) sin θ(5 cos2 θ − 1) cos ϕ C31− = ( 6/4)(5 cos2 θ − 1) sin ϕ
√ √
3 C32+ = ( 15/2) cos θ sin2 θ cos 2ϕ C32− = ( 15/2) cos θ sin2 θ sin 2ϕ
√ √
3 C33+ = ( 10/4) sin3 θ cos 3ϕ C33− = ( 10/4) sin3 θ sin 3ϕ
In complete analogy the real angular momentum states are defined by
i(p−1)/2
|J Mp = √ (−1)q |J M + p|J − M for 0 < M ≤ J (D.6)

2
|J 0+ = |J 0 and |J 0− = 0 for M = 0.
Note that the relations between real and complex unit polarization vectors (4.7) are
also constructed according to that scheme. And by inserting (B.20) into (D.5) we
obtain the real spherical harmonics

2k + 1
Ykqp (θ, ϕ) = Ckqp (θ, ϕ) where
4π

2(k − q)! q
Ckq+ (θ, ϕ) = P (cos θ ) cos(qϕ) for 0 < q ≤ k (D.7)
(k + q)! k

2(k − q)! q
Ckq− (θ, ϕ) = P (cos θ ) sin(qϕ) for 0 < q ≤ k
(k + q)! k
Ck0+ (θ, ϕ) = Pk0 (cos θ ) and Ck0− (θ, ϕ) ≡ 0 for q = 0,

q
with the associated L EGENDRE polynomials Pk which can be derived from (B.22).
Some explicit expressions for the renormalized real spherical harmonics Ckqp (θ, ϕ)
are given in Table D.1. Their orthogonality relations are
2π π
∗ 4π
dϕ Ckqp (θ, ϕ)Ck q p (θ, ϕ) sin θ dθ = δkk δqq δpp . (D.8)
0 0 2k + 1
Rotation of the real tensor operators, real states and real spherical harmonics is
achieved by (E.25) using the real rotation matrices (E.26)–(E.28).
D.3 Reflection Symmetry of Orbitals – Real and Complex Basis States 597
While the real spherical harmonics are eigenfunctions of 2z ,

2
L and L
2
L Ykqp = k(k + 1)2 Ykqp
2z Ykqp = q 2 2 Ykqp
L with q = 0, 1, . . . , k, (D.9)
they are neither eigenfunctions of Lz nor of L

x or L
y . However, the real spherical
harmonics and the corresponding real states (electron orbitals) are characterized by
a well defined reflection symmetry – not only in respect of the xy plane (which is
also a plane of reflection symmetry for the complex basis) but also in respect of the
xz and yz plane. Reflection of a wave function at the xz plane e.g. is equivalent
to replacing ϕ by −ϕ. In case of the complex basis this leads to Ykq (θ, −ϕ) =
∗ (θ, ϕ) = (−1)q Y
Ykq k−q (θ, ϕ). However, by applying this relation to the definition
of the real spherical harmonics (D.5)
one finds for a reflection at the xz plane

σv (xz)Ykqp = pYkqp with p = ±1, (D.10)
where we have introduced the reflection operator

σv (xz).
Often one wants to express (D.7) in Cartesian coordinates. We apply a very use-
ful relation communicated by C AOLA (1978). In our notation the so called solid
harmonics Ykq (x, y, z) are (renormalized):
Ckq (x, y, z)

4π
= Ykq (x, y, z) = r k Ckq (θ, ϕ) (D.11)
2k + 1

(k−q)/2
(−1)j (x + iy)j +q (x − iy)j zk−q−2j
= (−1)q (k − q)!(k + q)! .
22j +q (j + q)!j !(k − q − 2j )!
j =max(−q,0)
Inserting this into (D.5) leads to explicit expressions for the renormalized real solid
harmonics Ckqp . Table D.2 summarizes the most important cases.
Figure D.1 illustrates graphically the angular dependence of the three real basis
orbitals for k = = 1: |px , |py , and |pz (short: px , py and pz orbital, respec-
tively) and compares them to the usual complex basis orbitals |1 ±1 and |10. Ob-
viously, the real spherical harmonics are represented by dumbbell like states parallel
to the x-, y-, and z-axes of the atom, respectively. In contrast the complex basis con-
sists of two doughnut like orbitals (|1 ±1 with opposite sense of orientation) while
the |10 orbital is also dumbbell like and identical to |pz .
One may think of preparing these basis states by optical dipole excitation.
However, since electrons have also a spin, and m are typically not
good quantum numbers. Thus, a complete optical preparation of the orbitals shown
in Fig. D.1 is only possible in very special cases. If e.g. one can make use of a
Table D.2 Renormalized k p = +1 p = −1

real solid harmonics Ckq for
k = 1 to 3 0 C00+ = 1 C00− = 0
1 C10+ = z C10− = 0
1 C11+ = x C11− = y
2 C20+ = (3z2 − r 2 )/2 C20− = 0
√ √
2 C21+ = 3zx C21− = 3zy
√ 2 √
2 C22+ = 3(x − y 2 )/2 C22− = 3xy
3 C30+ = z(5z2 − 3r 2 )/2 C30− = 0
√ √
3 C31+ = 6x(5z2 − r 2 )/4 C31− = 6y(5z2 − r 2 )/4
√ √
3 C32+ = 15z(x 2 − y 2 )/2 C32− = 15zxy
√ √
3 C33+ = 10x(x 2 −3y 2 )/4 C33− = 10y(3x 2 −y 2 )/4
⊕z ⊕z
Fig. D.1 Angular part of
atomic p orbitals (spherical p =+1
harmonics) in the complex z
(top row) and real (bottom |+1〉 |0〉 |-1〉
row) basis. Plotted are the
squared moduli |Y1q |2 and
|Y1q± |2 , respectively. The
colour shading indicates x y x y x y
regions of different signs of
the functions. The ⊕ and
signs indicate positive and
negative reflection symmetry
in respect of the xy plane,
⊕z p =+1
z
p =+1 ⊕z p = – 1
| px 〉 | pz 〉 | py 〉
while reflection symmetry in
respect of the xz plane
according to (D.10) is
characterized by red p = +1
and p = −1 x y x y x y
1S → 1 P1 transition, it is indeed possible to prepare all five different basis states

0
individually by optical dipole excitation. In such a case, for example in a two elec-
tron system like He, the electron spin is compensated by another electron in the
system, but only one electron is excited:
(a) The complex basis set requires circularly polarized light for its preparation: left
and right hand circularly polarized, propagating along the z-axis to excite the
|1 +1 (equivalent to Y1+1 ) and the |1 −1 (equivalent to Y1−1 ) states, respec-
tively. Linearly polarized light propagating perpendicularly to the z-axis and
with its E vector aligned parallel to the z-axis excites the |10 state (equivalent
to Y10 ).
(b) The real basis set requires linearly polarized light for its preparation: the |pz
state (identical to |10) is excited as just described, while the preparation of |px
D.4 Reflection Symmetry in the General Case 599
Fig. D.2 Schematic z z z

illustration of a reflection
^
σv (xz) in the xz plane being
constructed from an inversion y
P y y
at the origin (P ) and a x x x
rotation through π about the
^
y-axis σv (xz)
and |py requires linearly polarized light with its E vector parallel to x and y,
respectively.
Generally speaking, the real basis functions are the basis of choice when the sign
of the angular momentum is irrelevant, i.e. whenever there is no specific preferred
orientation. Thus, they are relevant if external electric fields are present. They play
a particularly important role in molecular physics and quantum chemistry as dis-
cussed in detail in Chaps. 3–4 of Vol. 2, but also in collision problems. There, the
electrostatic field between different, neighbouring atoms defines a suitable z-axis
and is typically very strong so that spin quantum numbers can be treated as a mere
afterthought. Thus, the orbital angular momentum quantum numbers and the abso-
lute value of their projection onto this axis become good quantum numbers. Real
atomic orbitals (AO’s), as depicted in the bottom row of Fig. D.1, and linear com-
binations of them – attached to different atoms – are the basis for a quantitative
treatment of electronic wave functions in molecules.
Reflection symmetry is also an important property in the context of collision
problems. As we shall discuss in Chaps. 6–8, Vol. 2, reflection symmetry in respect
of the scattering plane is conserved during a binary collision for the combined wave
function of the interacting particles. Thus, either reflection symmetry of both parti-
cles remains constant during the collision, or both particles change their reflection
symmetry in respect of the collision plane.
D.4 Reflection Symmetry in the General Case
Since reflection symmetry is such an important property of atomic and molecular

states, we now generalize the concept. So far, the discussion was restricted to the
orbital part of the state vectors, i.e. to the integer values of the total angular momen-
tum J . In these cases reflection symmetry is an intuitively obvious property of the
wave functions. However, it is possible to extend this concept to half integer angular
momenta as well.
We start by noting that a reflection σv in respect of a given plane may be viewed
as an inversion at the origin with subsequent rotation through an angle π around
the axis perpendicular to this plane. This is illustrated in Fig. D.2. Inversion at the
origin implies, that the parity operator P multiplies the state vectors |J M with
(−1)λ , where λ is an odd or even integer depending on whether the parity of the
whole system is odd or even (typically determined by the orbital angular momentum
of the wave function). The rotation through π is achieved with the help of rotation
matrices described in Appendix E. Thus, the state |J M after reflection in the xy

plane becomes

J

σv (xy)|J M = (−1)λ DJM M (π, 0, 0) J M = e−iMπ (−1)λ |J M
M
= (−1)λ+M |J M. (D.12)
We note here in passing that with this relation the |+1 and |−1 p states in Fig. D.1
have both positive reflection symmetry in respect of the xy plane, while the |0 state
has negative reflection symmetry – as intuitively obvious.
Reflection at the xz plane leads to

σv (xz)|J M = (−1)λ DJM M (0, π, 0) J M
M
= (−1)λ d−MM
J
(π)|J −M = (−1)λ+M+J |J −M. (D.13)
Here we have used the symmetry relation (E.9) for the reduced rotational matrix.
From (D.12) and (D.13) we see that the standard complex |J M representation are
eigenstates of the xy plane reflection operator but not of the operator for reflection
in the xz plane. In analogy to (D.5) one may, however, construct also for the general
case (J integer or half integer) states of specified reflection symmetry in respect of
the xz plane:

|J Mp = v(p, M) (−1)M |J M + (−1)λ+J p|J −M with (D.14)

⎧
⎨ 1/2√ for M = 0
v(p, M) = 1/ √ 2 for 0 < M ≤ J and p = 1 or +i (D.15)
⎩
−i/ 2 for 0 < M ≤ J and p = −1 or −i.
Here p = ±(−1)J is the eigenvalue of the reflection operator σv (xz) in respect of

the xz plane. Applying (D.13) to (D.14) one easily verifies that |J Mp are orthonor-
malized eigenstates of
σv (xz):
σv (xz)|J Mp = p|J Mp.

(D.16)
For integer values of J = k, M = q and λ = J the previous relations (D.5) are

recovered, and p = ±1. For half integer values of J the eigenvalues of the σv (xz)
reflection are obviously p = ±i. The same eigenvalues are found for reflection in
the xy plane. However, half integer states with ±M belong to different reflection
symmetry, while for integer values of J (spherical harmonics) reflection symmetry
depends on |M|.
In general, the |J Mp states are not eigenstates of any of the components of
the angular momentum operator. The matrix elements of Jx , Jy , and Jz may be
derived from the definition (D.14) with (B.4) and (B.14)–(B.17). In general one has
to distinguish different cases such as J, M = 0, 1/2, and 1 as well as p = ±1 or ±i.
Thus, we note here only a few special aspects.
D.4 Reflection Symmetry in the General Case 601
1. The states defined by (D.14) are eigenstates of Jz2 . One easily derives

+1 for p = +1 or +i

Jz |J Mp = iM J M(−p) ×
−1 for p = −1 or −i
so that Jz2 |J Mp = M 2 2 |J Mp. (D.17)
2. Jz changes the reflection symmetry from +(−1)J to −(−1)J and vice versa, and
so does Jx :

Jx |J Mp = a(M) J (M + 1)(−p) + a(−M) J (M − 1)(−p) (D.18)
as one verifies for J ≥ 1 and M > 0 easily with some algebra. In contrast Jy
does not change reflection symmetry:

Jy |J Mp = a(M) J (M + 1)p − a(−M) J (M − 1)p (D.19)
where a(M) is typically1 given by

a(M) = √ J (J + 1) − M(M + 1).
2
3. As specific examples, we have already discussed the p orbitals |px = |11+,
|py = |11− and |pz = |10+ depicted in the lower part of Fig. D.1. Without
proof we note here in passing the relations:
Jy |px = −i|pz

Jy |pz = +1|px (D.20)
Jy |py = 0.
4. The simplest, and somewhat exceptional case with half integer J is a pure spin
state with λ = 0, J = 1/2, describing e.g. an electron in a 1 S1/2 state. The basis
states in the |J M representation are |1/2 1/2 and |1/2 −1/2, with spin point-
ing in the +z- and −z-direction, respectively. Reflection on the xy plane gives
according to (D.12)
% % % %
1 1 1 1 1 1 1 1

σv (xy)
= i and
σv (xy) − = −i − . (D.21)
22 22 2 2 2 2
We see that the up and down spin states have opposite reflection symmetry in
respect of the xy plane. The corresponding states with defined xz reflection sym-
metry are obtained from (D.14) (λ = even) with p = ±i:
1 These formulas hold for all J ≥ 1 and M ≥ 1. The other cases are easily derived individually
from the definition (D.14) with (B.4) and (B.14)–(B.17).

% %
1 1 1 1 1

|+i = √ i − − (D.22)
2 22 2 2
% %
1 11 1 1
|−i = √ i
+ − . (D.23)
i 2 22 2 2
These states are identical to (E.17) and (E.18), respectively, obtained by coor-
dinate rotation for a spin state pointing into ±y direction. Reflection at the xz
plane gives with (D.13):

σv (xz)|+i = i|+i and
σv (xz)|−i = −i|−i. (D.24)
In this particular case (and only in this one), these xy reflection symmetric states
are also eigenvectors of Jy . With (B.4) and (B.14)–(B.17) one easily verifies that

Jy |±i = ± |±i. (D.25)
2
We finally apply the concept of reflection symmetry to optical transitions treated
in detail in Chap. 4. In Sect. 4.1.2 we have introduced linear (ex , ey ) and circular
(e+1 , e−1 ) polarization vectors. We may write |ex , |ey and |e+1 , |e−1 as the real
and complex representation of the corresponding photon states, respectively. Then
the definitions (4.4)–(4.7) are in complete agreement with (D.14). Since for the pho-
ton J = λ = 1, M = ±1, we have p = +1 for |ex and p = −1 for |ey , i.e. |ex
and |ey have positive and negative reflection symmetry in respect of the xz plane.
Since the (fully quantized) Hamiltonian for the system photon + atom is invariant
under reflection at any plane through the centre of the atom, the reflection symmetry
of the state vectors describing the combined system must conserve reflection symme-
try. Depending on whether we use light which is polarized in the x- or y-direction,
the atom changes or conserves its reflection symmetry in an optical transition as
indicated by the following scheme:
|J Mp; ex ←→ |J Mp; . . .

|J Mp; ey ←→ J M(−p); . . . .
For example, the prototype 1 S0 ↔ 1 P1 transition induced by light linearly polarized

in the x-direction induces no change in the reflection symmetry: The 1 S0 state has +
reflection symmetry in respect of the xz plane as well as the 1 P1 dumbbell pointing
into x-direction (see Fig. D.1). The y-polarized light excites the dumbbell pointing
into the y-direction, having negative reflection symmetry.
A somewhat less trivial example is depicted in Fig. D.3. In a 2 S1/2 → 2 P1/2
transition the initial state |Ja = |+i corresponds to (D.22), with its spin pointing
into the +y-direction it has p = +i reflection symmetry in respect of the xz plane.
Since after the excitation to a P state, the parity of the atom changes (λ = 0 → 1),
the final state |Jb with angular momentum pointing into +y-direction has now
p = −i symmetry. When exciting with ey light, the combined system |Ja |ey prior
Fig. D.3 Illustration of z z z z

reflection symmetry changing
and non-changing processes ⎢Ja ⎢Jb ⎢Ja ⎢–Jb
in a 2 S1/2 ↔ 2 P1/2 transition y y e y y
x
induced by light linearly ey
polarized in x- and x x x x
y-directions, respectively k k
2S
1/2
→ 2P1/2 2S
1/2
→ 2P1/2
to the transition has +i × (−1) = −i reflection symmetry, thus the final state must
also have −i symmetry, which corresponds to |Jb pointing into +y-direction. In
contrast, for excitation with ex polarized light, the combined initial system |Ja |ex
has +i × (+1) = i symmetry, which must be conserved and corresponds to reversing
the orientation of the spin into |−Jb .
Circularly polarized photons |e+1 or |e−1 propagating into z-direction have
both positive reflection symmetry in respect of the xy plane (in analogy to the |+1
and |−1 p states in Fig. D.1) and cannot change this reflection symmetry of the
atomic states. Formally one sees this from (D.12), since in a dipole transition both λ
and M change by ±1 in respect of the “photon frame” where z k. Thus, (−1)λ+M
remains constant during the excitation process and reflection symmetry in respect
of the xy plane does not change.
good quantum number: ‘Quantum number for eigenvalues of such observables that
may be measured simultaneously with the H AMILTON operator (see Sect. 2.6.5)’.
References
C AOLA, M. J.: 1978. ‘Solid harmonics and their addition theorems’. J. Phys. A, Math. Gen., 11,
L23–L25.
Coordinate Rotation
E
We compile here the most important formulas for rotation of coordinate systems
and their consequences on angular momentum states and tensor operators – without
going into details of the derivation.
E.1 EULER Angles
One specifies a coordinate rotation by three E ULER angles (α, β, γ ). As shown in

Fig. E.1 the rotation is performed in three steps:

(xyz) → x y z → x y z → x # y # z# .
First, one rotates the system around its original z-axis (z = z) through an angle α.
The following rotation through an angle β around the new y axis (y = y ) brings
z into the direction z and x into direction x . The final rotation through an angle
γ is around the thus tilted z = z# axis (x → x # and y → y # ).
Fig. E.1 Definition of the z, z'

Euler angles (α, β, γ ) for
rotation of a coordinate z'', z# β y#
system xyz
γ y'
α y''
y
α
β γ
x x#
x' x''

606 E Coordinate Rotation
E.2 Rotation Matrices
The operator achieving this rotation is derived from the angular momentum opera-
tor
J:

D(αβγ ) = exp(−iγ Jz ) exp(−iβ Jy ) exp(−iα Jz ).
The corresponding rotation matrix elements, more precisely the matrix elements
J of the rotation group, may be derived with
of the irreducible representation D
some angular momentum algebra (following the notation of B RINK and S ATCHLER,
1994),1 and are written as

DJMN (αβγ ) =
J M|D(αβγ )|J N = exp(−iαM)dMN
J
(β) exp(−iγ N ), (E.1)
with the reduced rotation matrix:
[(J + M)!(J − M)!(J + N )!(J − N )!]1/2

J
dMN (β) = (−1)t
t
(J + M − t)!(J − N − t)t (t + N − M)! (E.2)
× (cos β/2)2J +M−N −2t (sin β/2)2t+N −M .
Special cases:

4π
DJM0 (αβγ ) = CJ∗ M (β, α) = Y ∗ (β, α) (E.3)
2k + 1 J M

(J − M)! M
J
dM0 (β) = (−1)M P (cos β) if M > 0 (E.4)
(J + M)! J
J
and d00 (β) = PJ (cos β). (E.5)
We note some important symmetry properties
DJMN (αβγ )∗ = (−1)M−N DJ−M−N (αβγ ) = DJN M (−γ − β − α), (E.6)

J
dMN (β) = (−1)M−N dNJ M (β) = d−N
J
−M (β) = dN M (−β)
J
(E.7)

= (−1)J −M dM−N
J
(π − β) = (−1)J +M dM−N
J
(π + β). (E.8)
J
dMN (π) = (−1)J +M δ−MN and (E.9)
J
dMN (0) = δMN = (−1)2J dMN
J
(2π). (E.10)
1 Here the coordinate system is rotated. An alternative convention, also found in the literature, is to
rotate the states.

E.2 Rotation Matrices 607
Explicitly we communicate formulas for the frequently used cases J = 1/2, J = 1,

and J = 2 according to B RINK and S ATCHLER (1994):

1 1 β 1 1 β
d 12 1 = d 2 1 1 = cos d 2 1 1 = −d 12 1 = sin (E.11)
2 2 − −
2 2 2 − 2 2 2 2− 2

β 2 β
d11 = d−1 −1 = cos
1 1 2 d1−1 = d−11 = sin
1 1
2 2 (E.12)
sin β
d01 = d−10 = −d0−1 = −d10 = √
1 1 1 1 d00 = cos β.
1
2
2
d22 = d−2−2
2
= cos4 (β/2) (E.13)
2 = d2 = d2
−20 = d0−2
2 = −d 2
−1−2 0 = −d−2−1 = d12
d20 2 2 2
02 d21
√
= ( 3/8) sin2 β = − sin β(1 + cos β)/2
2
d2−1 = d1−2
2 0 = −d 2
−21 = −d−12
2
2
d2−2 = d−22
2 = sin4 (β/2)
= sin β(1 + cos β)/2
2
d11 = 2
d−1−1 2
d1−1 = d−11
2
= (2 cos β − 1)(1 + cos β)/2 = (2 cos β + 1)(1 − cos β)/2

2 = d2
0−1 = −d01 = −d−10
d10 2 2
2 = (3 cos2 β − 1)/2
d00 √
= ( 3/2) sin β cos β.
An angular momentum state |J N # in the new system may be expressed by

eigenstates |J M in the original system as:

J |J N =
|J N# = D
|J M
J M|D(αβγ )|J N = |J MDJMN (αβγ )
M M

= exp(−iγ N ) |J M exp(−iαM)dMN
J
(β). (E.14)
M
The components Tkq (θ # , ϕ # ) of tensor operators of rank k (e.g. Ykq or a vector with
k = 1) can be expressed by tensor components in the old system

Tkq θ # , ϕ # = Tkq (θ, ϕ)Dkqq (αβγ )
q

= exp −iγ q k
Tkq (θ, ϕ) exp(−iαq)dqq (β) (E.15)
q
with θ , ϕ and θ # , ϕ # being the angles in the old and new system, respectively.
We illustrate the procedure by a particularly simple and important example,
a spin s = 1/2 state |1/2 1/2# pointing into the ϕ = α, θ = β direction in the orig-
1/2
inal coordinate frame xyz. Inserting for this case dMN (β) from (E.11) into (E.14)
we obtain:
(a)
(b)
Fig. E.2 Rotation to describe a spin s pointing into (a) +y-direction, (b) +x-direction
%# % %
1 iγ iα β 1 iα β 1
= exp − exp − cos + exp sin − .
2 2 2 2 2 2 2 2
(E.16)
(For simplicity of writing we have dropped here J = 1/2.) The third rotation angle
γ around the final z# axis is somewhat arbitrary and just contributes a free phase
factor.2 Figure E.2(a) indicates the rotation angles for one specific case where the
spin s points into the +y-direction of the (xyz) coordinate system. Thus, the oblig-
atory rotation angles are α = ϕ = π/2 and β = θ = π/2. We choose γ = −3π/2,
make use of (E.11)–(E.13), and thus obtain from (E.16) for this particular spin state
% % %
1 #(y) 1 1 1
+ = √ i + − − . (E.17)
2 2 2 2
If the spin s points into the −y-direction, we make exactly the same rotation and
find from (E.14)
% % %
1 #(y) 1 1 1
− = √ i + + − (E.18)
2 i 2 2 2 .
Somewhat more compact, we designate the spin states parallel and antiparallel to
the y-axis with by |α(y) and |β(y) , respectively, and those which refer to the z-axis
with |α and |β. Equations (E.17) and (E.18) may then be written:
1
1
|α(y) = √ i|α − |β and |β(y) = √ i|α + |β . (E.19)

2 i 2
2 Note, however, that for spin

1/2 this rotation angle is defined modulo 4π – rather than modulo 2π
(one more turn around the z axis changes the sign). For example, the angle γ = −3π/2 in Fig. E.2
has not the same effect as γ = π/2.
E.3 Entangled States 609
For completeness we also describe a state where the spin s points into the ±x-
direction. As illustrated in Fig. E.2(b) the E ULER angles in this case are (0, π/2, π)
and we obtain
%
1 #(x) ∓1
± = √ |α ± |β . (E.20)

2 2
All these states are of course eigenstates of the squared spin angular momentum
S 2 , with spin quantum number s = 1/2. The eigenvalue of
S 2 are 2 s(s + 1) =

3 /4. And specifically |α and |β are also eigenstates of Sz , the spin projection
2
onto the z-axis, with eigenvalues /2 and −/2, respectively. What about the states
|±1/2(x,y) ?
Here is a little exercise for the active reader, which can be solved with a few
lines of algebra (for complex quantities): Using (B.4), (B.16) and (B.17), show that
the spin states |α(y) and |β(y) are indeed eigenstates of the spin component in y
direction with eigenvalues ±/2:

Sy |α(y) = |α(y) and
Sy |β(y) = − |β(y) . (E.21)
2 2
And the same holds of course for the corresponding spin states pointing in ±x-
direction.
E.3 Entangled States
For many-particle systems we have to construct spin functions which account for
the fact that identical particles are indistinguishable. We have discussed this in the
main text on several occasions, see e.g. Table 6.1 in the context of fine structure and
Sect. 7.3 where specifically the He atom is treated. Let us take the latter example,
i.e. the two electrons in the He ground state (1s)2 1 S0 , or any singlet state of two
electrons in the continuum after ionization (with a symmetric spatial wave function).
The two spins of the electrons are anti-parallel and since we cannot distinguish
which of these two fermions has which spin we have to construct an antisymmetric
description of their joint state, according to (7.36)
0
χ = √1 α(1)β(2) − β(1)α(2) , (E.22)

0
2
where the numbers in brackets refer to electron (1) and electron (2), respectively.
Obviously, this state of the two electrons is inseparable, i.e. it cannot be written
as product of two wave functions of the individual electrons. One calls such states
entangled.
Equation (E.22) refers to a particular coordinate frame and |α and |β reflect
the spin components with respect to its z-axis. The total (spin) angular momentum
operator is
S = S1 +
S 2 , and the singlet state (E.22) is constructed such that the
respective eigenvalues of S and
2
Sz are zero:3
2
Sz χ00 = (
S2z ) χ00 = 0 and
S1z + S χ00 = 0. (E.23)
One may now be curious what happens if we define this entangled, antisymmetric
spin state with respect to another axis, say the y-axis. This may be done in complete
analogy to (E.22) from spin states with angular momentum parallel and antiparallel
to the y-axis:
0
χ = √1 α(1)β(2) (y) − β(1)α(2) (y) . (E.24)

y
2
In full analogy to (E.23) we have now Sy |χy0 = 0, i.e. the projection of the total spin
onto the y-axis is also zero. The relation (E.19) between the |α(y) and |β(y) states
and the |α and |β states parallel to the z-axis may now be inserted into (E.24):
with just a few lines of algebra (in which many terms cancel) one recovers again
(E.22), i.e. the singlet state with respect to the z-axis. Thus, the definition of this
entangled state does not depend on the coordinate axis and its angular projection is
zero in all coordinate systems.
So much about coordinate rotation for entangled states. Entanglement is a very
active field of current research with far reaching consequences, not only for funda-
mental conceptual and philosophical reasons (dating back to the famous E INSTEIN ,
ROSEN , P ODOLSKY 1935 paper, quoted by now over 5000 times), but also in view
of a number of potential future applications such as quantum cryptography or quan-
tum computation. We cannot enter here in a detailed discussion of this wide field
but refer the reader to some relatively recent reviews and references quoted there
(T ICHY et al., 2011; H ORODECKI et al., 2009; R AIMOND et al., 2001), see also the
respective chapters in B LUM (2012).
E.4 Real Rotation Matrices
For reference we also communicate the rotation procedure (FANO, 1960) for the
real harmonics, real states and real tensor operators as defined in Appendix D. In
this case, the transformation is achieved by

# #
Tkq p θ , ϕ = Tkqp (θ, ϕ)Dkqp,q p (αβγ ) (E.25)
qp
3 The first relation is obvious, since each of the operators S1z and
S2z acts only onto one of the
states which have the eigenvalues ±/2, i.e. they compensate each other. The latter relation may
easily be verified as an exercise with the help of (B.8) and (B.17).
References 611
with p, p = ±1. The real rotation matrices are obtained by applying the complex
rotation (E.15) onto the defining equations (D.5) and finally back-transformation to
the real basis. One obtains:4
For k ≥ q, q > 0:
(E.26)
Dkqp,q p (αβγ )
⎧ k
⎪ k
⎪ (−1)q dqq (β) cos(αq + γ q ) + p dq−q (β) cos(αq − γ q )
⎪
⎨
if p = p
= (−1)−q
⎪
⎪ (−1)q p dqq
k (β) sin(αq + γ q ) + d k

q−q (β) sin(αq − γ q )
⎪
⎩
if p = p
For q or q = 0: (E.27)

√ k cos(qα + q γ ) if p = p
Dkqp,q p (αβγ ) = (−1)−q+q 2dqq (β)
sin(qα − q γ ) if p = p
specifically Dkqp,0+ (αβγ ) = Ckqp (β, α) (see Eq. (D.7))
For q = q = 0: Dk0+,0+ (αβγ ) = d00

k
(β). (E.28)
References
E INSTEIN, A., B. P ODOLSKY and N. ROSEN: 1935. ‘Can quantum-mechanical description of
physical reality be considered complete?’ Phys. Rev., 47, 777–780.
FANO, U.: 1960. ‘Real representations of coordinate rotations’. J. Math. Phys., 1, 417–423.
H ERTEL, I. V. and W. S TOLL: 1978. ‘Collision experiments with laser excited atoms in crossed
beams’. In: ‘Adv. Atom. Mol. Phys.’, vol. 13, 113–228. New York: Academic Press.
H ORODECKI, R., P. H ORODECKI, M. H ORODECKI and K. H ORODECKI: 2009. ‘Quantum entan-
glement’. Rev. Mod. Phys., 81, 865–942.
R AIMOND, J. M., M. B RUNE and S. H AROCHE: 2001. ‘Colloquium: Manipulating quantum en-
tanglement with atoms and photons in a cavity’. Rev. Mod. Phys., 73, 565–582.
T ICHY, M. C., F. M INTERT and A. B UCHLEITNER: 2011. ‘Essential entanglement for atomic and
molecular physics’. J. Phys. B, At. Mol. Phys., 44, 192001.
4 See also H ERTEL and S TOLL (1978), Eq. (15) (some small typos there have been corrected here).
Multipole Expansions and Multipole Moments
F
One often needs suitable approximations for potentials which at large distances are
nearly symmetric around a centre, but not completely. For scalar as well as for vector
potentials, multipole expansions may be derived. We treat here the important case
of an electrostatic potential arising from a charge distribution localized in a small
region around the origin – as e.g. encountered when describing the interaction of
atomic nuclei with the electron charge cloud of an atom (see Fig. 9.12 in Chap. 9).
In the final subsection we shall also introduce a more general definition of multipole
tensor operators and multipole moments.1
F.1 Laplace Expansion
We first note that the inverse distance between two points r and r in space may be
expanded for r r into a power series of x = r /r:
1 1 −1/2
= 1 − 2x cos θ + x 2 (F.1)
|r − r | r

1 3 1 5 3
= 1 + x(cos θ ) + x 2 cos2 θ − + x3 cos3 θ − cos θ · · ·
r 2 2 2 2
where θ is the angle between r and r . With (B.24) we identify the angle dependent
terms in brackets as L EGENDRE polynomials. With this result in mind, we commu-
nicate the L APLACE expansion which holds for r < r:
∞
r k
1
= Pk (cos θ )
|r − r| r k+1
k=0
1 The term “multipole moments” is used in the literature for a variety of slightly different defini-
tions. As far as necessary for distinction, we shall add some specification, indicated in (brackets).

614 F Multipole Expansions and Multipole Moments
∞
∞
r k ∗ r k (r) (r )
k
= C kq (θ, ϕ)C kq θ , ϕ = C · Ck (F.2)
r k+1 r k+1 k
k=0 q=−k k=0
∞

r k
k

= Ckqp (θ, ϕ)Ckqp θ , ϕ .
r k+1
k=0 q=0,p=±1
In the second line of (F.2) we have made use of the addition theorem (C.22) for
the renormalized spherical harmonics, with θ , ϕ and θ , ϕ being the angles of the
position vectors r and r , respectively. In the following equality we have made use
(r) (r )
of (C.21) and the scalar product notation (C.20) for the two tensors Ck and Ck .
The third line of (F.2) introduces the real (renormalized) spherical harmonics as
defined in Appendix D.3.
F.2 Electrostatic Potential
With these relations we write the electrostatic interaction energy dV12 (r, r ) of a
charge dq, located at a position r , with a point charge −e located at r
∞
1 −edq 1 −e (r) k (r )
dV12 r, r =
= Ck · r dq Ck . (F.3)
4πε0 |r − r| 4πε0 r k+1
k=0
For an extended electric charge with density ρ(r ), localized around the origin, the
charge element is dq = ρ(r )d3 r , and the total interaction energy with the point
charge −e is obtained from

−e ρ(r ) 3
V (r) = dV12 r, r = d r. (F.4)
4πε0 |r − r|
With (F.3) we may write this as a multipole expansion
∞
−e 1
k
V (r) = Qkq Ckq (θ, ϕ) or (F.5)
4πε0 r k+1
k=0 q=−k
∞
−e 1
k
in real form = Qkqp Ckqp (θ, ϕ), (F.6)
4πε0 r k+1
k=0 q=0,p=±1
with (charge) multipole moments

Qkq = Ckq θ , ϕ r k ρ r d3 r , or (F.7)

Qkqp = Ckqp θ , ϕ r k ρ r d3 r = Ckqp r ρ r d3 r , (F.8)
F.2 Electrostatic Potential 615
where we have used in the second row for abbreviation the renormalized real solid
harmonics Ckqp as introduced in Appendix D.3.
These multipole expansions, derived from (F.3), are most appropriate if r r.
Thus, it is suitable e.g. for describing the field of an atomic nucleus as seen by an
electron far away from the nucleus (i.e. for ≥ 1), or for the far field of an atom in
a well defined polarization state (with ≥ 1).
The total charge is given by

q = Q00 = ρ r d3 r . (F.9)
For an electronic charge cloud of an atom with N electrons it is q = −N e, and for

an atomic nucleus with atomic number Z (protons in the nucleus) we have q = Ze.
If the charge distribution can be described by an electronic or nuclear wave func-
tion as ρ(r ) = q|ψnm (r )|2 = q|Rn (r )Cm (θ , ϕ )|2 the angular part of the ma-
trix elements in (F.7) may be evaluated as described in Appendix C.2.2 – if nec-
essary applying the recoupling rules from Appendix C.3. In this case, we find with
(C.30) that only even multipole moments are nonvanishing: k = 0 (monopole), k = 2
(quadrupole), k = 4 (octupole), etc.
More generally, for an arbitrary charge distributions, convenient expressions for
the real multipole moments (F.8) are obtained with the renormalized real solid har-
monics (D.11). The components of the dipole moment are:

Dz = Q10+ = z ρ r d3 r Q10− = 0
(F.10)

Dx = Q11+ = x ρ r d3 r

Dy = Q11− = y ρ r d3 r .

If only positive or only negative charges are involved, the dipole moments are made
to disappear by suitable choice of the origin, thus defining a charge centre. They
also disappear if both charges have the same centre (characteristic for atoms, unless
they are placed in an electric field, see Sect. 8.2.8). In contrast, if positive and neg-
ative charges with different centres are to be described (typical for polyatomic and
heteronuclear diatomic molecules) the dipole moment is finite.
With (F.8) and Table D.2 the real quadrupole moments are:

1 2
Q20+ = 3z − r 2 ρ r d3 r Q20− = 0
2
√ 3 √ 3
Q21+ = 3 z x ρ r d r Q21− = 3 zyρ r d r (F.11)
√ √
3 2 3
Q22+ = x − y 2 ρ r d3 r Q22− = x y ρ r d3 r .
2 2
Note that a variety of slightly different terminologies is used in the literature.2 In

nuclear physics one defines (assuming symmetry around the nuclear z-axis) the
nuclear quadruple moment

Q= 3z 2 − r 2 ρ r d3 r = 2Q20+ . (F.12)
Explicitly, in Cartesian coordinates the potential expansion (F.6) reads

−e q D · r 1 C2qp (x, y, z)
V (r) = + 3 + Q2qp + · · · . (F.13)
4πε0 r r 2 qp r5
The components (F.10) of the electric dipole moment D are zero for charges cen-
tred at the origin, while the quadrupole moments Q2qp according to (F.11) are fi-
nite for an anisotropic charge distribution. The renormalized real solid harmonics
C2qp (x, y, z) are found in Table D.2.
F.3 Multipole Tensor Operators
Closely related to the (charge) multipole moments just discussed, but without any
reference to the charge of the particles, one defines irreducible spatial multipole
tensor operators of rank k. They are constructed from the position vector and have
the components
Qkq (r) = r k Ckq (θ, ϕ) = Ckq (x, y, z) (F.14)

for −k ≤ q ≤ k. (F.15)
using again the (renormalized) solid harmonics (D.11). They may also be written as
real quantities according to (D.5):
Qkqp (r) = r k Ckqp (x, y, z) = Ckqp (x, y, z) (F.16)

for 0 ≤ q ≤ k and p = ±1. (F.17)
For explicit expressions we refer to Table D.2. General rules for tensor operators
have been laid out in Appendix C.
2 E.g.
following JACKSON (1999), in classical electrodynamics one usually expands in terms of the
standards spherical harmonics, multiplying the terms in the sum (F.7) by 4π/(2 + 1), so that the
(complex) multipole moments are given as

∗
qm = Ym (Θ, Φ)R ρ(R)d3 R.
F.3 Multipole Tensor Operators 617
The expectation values

Qkq , i.e. the matrix elements
γ J M|Q2q |γ J M aver-
aged over the population probabilities w(M) of |γ J M states, are called (spatial)
multipole moments:

Qkq = r 2 w(M)
J M|Ckq (θ )|J M. (F.18)
M
They characterize the particle distribution (e.g. for the protons in an atomic nucleus,
for the electrons in an atom, or for electrons and nuclei in a molecule).
For a given angular momentum J of a quantum state the above definitions (F.14)
and (F.16) allow to construct multipole tensor operators and multipole moments of
rank 0 ≤ k ≤ 2J . They all have a well defined parity
kq (r) = (−1)k Qkq (r)
PQ (F.19)
but also a reflection symmetry in respect of the xy plane (see also Appendix D.4):
σv (xy)Qkq = (−1)k+q Qkq .

(F.20)
Here σv (xy) is the reflection operator in respect of the xy plane.

The real tensor operators (F.16) and the corresponding multipole moments often
allow a more flexible and self evident interpretation of physical situations. They are
constructed such that, in addition to parity (F.19) and reflection symmetry in respect
of the xy plane (F.20), they also have a well defined reflection symmetry p = ±1 in
respect of the xz plane:

σv (xz)Qkqp = pQkqp . (F.21)
They are appropriate tools to express symmetries e.g. in molecules and interaction
processes such as excitation by photons or collisions. For rotations of the real mul-
tipole moments in space (E.25)–(E.28) may be used.
F.3.1 The Quadrupole Tensor
Most commonly used is the quadrupole tensor Q2 with its components Q2q =
C2q (r, θ, ϕ) according to Table D.2. Higher moments become increasingly com-
plicated. If the quantum state |J M of an object is known exactly, the components
of the quadrupole moment are obtained from the respective matrix elements of the
quadrupole tensor Q2 . These matrix elements can be derived from the W IGNER -
E CKART theorem (C.9):

J −M
√ J J 2
γ J M Q2q |γ J M = (−1) 2J + 1
J Qk J (F.22)
M −M q
with
J Q2 J =
J C2 J
γ J |r 2 |γ J . (F.23)
Clearly, systems with angular momenta j = 0 or 1/2 do not have a quadrupole

moment, since the 3j symbols must satisfy the triangular relation δ(j j 2) = 1.
Specifically, the Q20 component of the quadrupole tensor is

3z2 − r 2 3 cos2 θ − 1
Q20 = C20 (θ ) = = r2 . (F.24)
2 2
With (B.58) its diagonal matrix element is
3M 2 − J (J + 1)

γ J M|Q20 |γ J M = √
J C2 J r 2 , (F.25)
(2J + 3)(J + 1)J (2J − 1)
and if the radial wave functions Rγj (r) are known, the radial matrix element
r 2
is obtained from
2
r =
γ J |r |γ J = r 4 |Rγj |2 dr.
2
The extrema of (F.25) for M = J and M = 0 are:

J (2J − 1)

γ J J |Q20 |γ J J =
J C2 J r 2 and (F.26)
(2J + 3)(J + 1)

J (J + 1)

γ J 0|Q20 |γ J 0 = −
J C2 J r 2 . (F.27)
(2J + 3)(2J − 1)
The reduced matrix element

J C2 J still depends on the coupling scheme of the
states under discussion. For LS coupling detailed expressions for the renormalized
spherical harmonics have been derived in Sect. C.3.1.
Specifically, for a quasi-one-fermion system with spin s = 1/2 (one active atomic
electron or nuclear proton) we use (C.55) to obtain the diagonal matrix elements:
$ %
1 1
j m Q20 j m
2 2
$ %
1 1
= j m C20 j m
γj |r 2 |γj
2 2

2j −m−1/2 j j 2 j j 2 2
= (−1) (2j + 1) r
m −m 0 1/2 −1/2 0
1 3m2 − j (j + 1) 2
=− r . (F.28)
4 j (j + 1)
For the last equality we have used (B.58) for the 3j symbols and the fact that j is
half integer, so that (−1)2j = −1. The highest (positive) value is found for m = 0,
the lowest (negative) value for m = j :
$ %
1 1

j 0 Q20 j 0 = r 2 /4 (F.29)
2 2
$ %
1 1 1 2j − 1 2
jj Q20 jj = − r . (F.30)
2 2 4 j +1
F.3 Multipole Tensor Operators 619
The expectation values of the quadrupole tensor, i.e. the (spatial) quadrupole
moments according to (F.18), may be related to the (charge) quadrupole moments
defined in Sect. F.2 by

Q2q = q
Q2q = r 2
J C2 J w(M)
J M20|J M. (F.31)
For a prolate (cigar shaped) charge distribution, dominated by low M states, (F.31)
leads to Q > 0, while an oblate (pancake like) distribution is characterized by large
|M| and Q < 0 (see e.g. Fig. 9.15).
In nuclear physics, the quadrupole moment of a nucleus (assuming cylindrical
symmetry around the z-axis) is
traditionally defined by Q = 2eZ

Q2q .
Note the factor 2eZ (overall charge eZ) as already introduced in (F.12): averaging
γ J M|Q20 |γ J M over state populations w(M) is equivalent to integration over

the charge distribution ρ(r) = eZ
|ψ(r)|2 . The probability density |ψ(r)|2 refers
to the total wave function for the charged particles of interest, while the population
of the states w(M) depends on the specific experiment.3 For a single active spin 1/2
particle system (i.e. a proton in the nucleus) in a pure |jj state, instead of (F.30)
the nuclear quadrupole moment thus reads (see also B OHR and M OTTELSON, 1998,
Eq. (3-27))
$ %
1 1 2j − 1
Qsp = 2 jj Q20 jj = −eZ
γj |r 2 |γj .
2 2 2j + 2
F.3.2 General Multipole Tensor Operators
Often it is desirable to use a more general form of irreducible tensor operators in

multipole expansions. Rather than constructing them from position operators one
may generate such operators from angular momenta. One straight forward pro-
cedure is to “polarize” the solid harmonics as introduced by FALKOFF and U H -
LENBECK (1950) for applications in nuclear physics. Using the normalization of
M ACEK and H ERTEL (1974) for the solid harmonics (FANO, 1960), these tensor
operators are obtained from

3
Tkq± = (Ji1 Ji2 . . . Jik )∇i1 ∇i2 . . . ∇ik Ckq± (r), (F.32)
i1 i2 ...ik =1
where ij = 1 to 3 stands for x, y and z. The angular momenta are given in a.u., i.e. in
units of . Applying this operation to the explicit expression for the (renormalized)
solid harmonics Table D.2 we obtain Table F.1.
3 For a general formalism see Chap. 9 in Vol. 2.

Table F.1 Multipole tensor operators constructed from angular momenta for k = 1 to 3 (only the
zero component is given for the octupole moment k = 3); for reference we also communicate the
relations with the FANO and M ACEK (1973) orientation (O1− ) and alignment parameters (A1+
and A2+ )
k p = +1 p = −1
0 T00+ = 1 T00− = 0
1 T10+ = Jz T10− = 0
1 T11+ = Jx T11− = Jy = J (J + 1)O1−
T20+ = (3Jz2 − T20− = 0
2
2 J )
√ √ √
2 T21+ = 3(Jz Jx + Jx Jz ) = J (J + 1) 3A1+ T21− = 3(Jz Jy + Jy Jz )
√ √ √
2 T22+ = 3(Jx2 − Jy2 ) = J (J + 1) 3A2+ T22− = 3(Jx Jy + Jy Jx )
T30+ = (15Jz3 − 9
J Jz + 3Jz )
2
3 etc.
The Tk0 (= Tk0+ ) components are obviously diagonal in J and M. Explicitly, the
matrix elements for k = 1 are
M

J M|T10 |J M = M = √
J T1 J (F.33)
J (J + 1)
and describe the orientation of the state (nonvanishing angular momentum). The
latter equality follows from the W IGNER -E CKART theorem (C.9) and (B.55). The
matrix elements of T20 characterize the alignment (quadrupole moment or the
anisotropy) of the charge density distribution in a given state:

J M|T20 |J M = 3M 2 − J (J + 1) (F.34)
2[3M 2 − J (J + 1)]
=√
J T2 J .
(2J + 3)(2J + 2)2J (2J − 1)
The latter follows again from the W IGNER -E CKART theorem, this time using
(B.58).
The reduced matrix elements for rank k = 1 and k = 2 follow directly from (F.33)
and (F.33), respectively:

J T1 J = J (J + 1) and (F.35)

J T2 J = (2J + 3)(J + 1)J (2J − 1). (F.36)
For an arbitrary rank k one finds (see e.g. M ACEK and H ERTEL, 1974, and refer-
ences given there; note, however, that the factor (2J + 1)−1/2 is specific for the
B RINK and S ATCHLER notation of the reduced matrix elements):

k! (2J + k + 1)!

J Tk J = k . (F.37)
2 (2J + 1)(2J − k)!
We point out that these (general) multipole tensor operators and their expectation
values, the (general) multipole moments, may be finite also for odd rank – in contrast
to the usual (charge or spatial) multipole moments as discussed above. This is a

direct consequence of their construction by angular moments, rather than by position
vectors.
The W IGNER -E CKART theorem provides a one to one relation between the ma-
trix elements of any irreducible tensor operator of rank k for a set of basis states
|j m – say for the spatial multipole tensor operators (F.14) Qkq constructed from
position coordinates – to any other irreducible tensor of the same rank in that basis
– say the Tkq multipole tensor operator. With (C.12) this relation is simply given by

J Tk J
J M Tkq |J M = J M Qkq |J M, (F.38)

J Qk J
with
J Qk J defined by (F.23). We emphasize that (F.38) also holds for the re-
spective expectation values (the multipole moments).
Often one is only interested in the expectation values (multipole moments) of
these tensors in an orbital angular momentum basis with sharp = (see e.g. Ap-
pendix D.2 in Vol. 2). We may then use the explicit expression (C.33) for the reduced
matrix elements of the renormalized spherical harmonics. These are nonvanishing
only for even k and we note that their sign is always negative – in contrast to (F.37)!
Thus, the multipole moments
Tkq (constructed from angular momenta) have the
opposite sign from
Qkq (which are built from spatial coordinates)!
Expectation values of these multipole tensor operators are widely used to char-
acterize anisotropy and orientation of atomic or molecular systems – in particular
if these cannot be described by pure states. Strictly speaking, they are measured in
units of k but one usually drops the unit. We shall refer to them as multipole mo-
ments as long as no confusion can arise with the (spatial) multipole moments con-
structed from position vectors.4 More details will be discussed in the context of the
density matrix in Chap. 9 and Appendix C, Vol. 2. In addition, we shall introduce
there yet another kind of irreducible tensor operators to characterize anisotropic
state populations, the so called statistical tensor operators. Their expectation values
are the state multipoles which again can be related by simple numerical factors with
any other irreducible representation of tensor operators, in analogy to (F.38).
is important to keep in mind that the sign of

Tk0 is opposite to that of
Qk0 . When speaking
4 It
about shapes of charge distributions we have to note that oblate implies

Q20 < 0 and
T20 > 0,
while a prolate shape is encountered if
Q20 > 0 and
T20 < 0.
References
B OHR, A. and B. R. M OTTELSON: 1998. Nuclear Structure, vol. 1: Single-Particle Motion. Sin-
gapore: World Scientific, reprint from 1969 edn., 471 pages.
FALKOFF, D. L. and G. E. U HLENBECK: 1950. ‘On the directional correlation of successive nu-
clear radiations’. Phys. Rev., 79, 323–333.
FANO, U.: 1960. ‘Real representations of coordinate rotations’. J. Math. Phys., 1, 417–423.
FANO, U. and J. H. M ACEK: 1973. ‘Impact excitation and polarization of emitted light’. Rev. Mod.
Phys., 45, 553–573.
JACKSON, J. D.: 1999. Classical Electrodynamics. New York: John Wiley & Sons, 3rd edn., 808
pages.
M ACEK, J. and I. V. H ERTEL: 1974. ‘Theory of electron-scattering from laser-excited atoms’.
J. Phys. B, At. Mol. Phys., 7, 2173–2188.
Convolutions and Correlation Functions
G
In this appendix all distribution functions f (x) are normalized such that
+∞
f (x)dx = 1. (G.1)
−∞
In other chapters of these textbooks a different type of normalization may be more

convenient and are used whenever appropriate, e.g. normalization to the maximum
max[f (x)] = 1.
G.1 Definition and Motivation
The mathematical operation called convolution quantifies the overlap between two
mathematical functions f1 (x) and f2 (x) as one is reversed and shifted in respect of
the other. A convolution is defined as
∞
(f1 ∗ f2 )(x) := f1 (ξ )f2 (x − ξ )dξ, (G.2)
−∞
which describes an important mathematical procedure, often required and used in

experimental physics and measuring techniques.
The cross-correlation of two (possibly complex) functions is defined by
∞
G(x) = (f1 f2 )(x) := f1∗ (ξ )f2 (ξ + x)dξ ≡ f1∗ (−x) ∗ f2 (x). (G.3)
−∞
Thus, both procedures are identical if one of the functions is even, f (−x) = f (x),
which is the case in most of the physical applications.1 If f1 ≡ f2 one calls G(x) =
(f f )(x) an autocorrelation function.
1 An alternative method to solve (G.3) is given by F (f1 f2 ) = 2π F (f1 )F (f2 ) where F (f ) de-
scribes the F OURIER transform of f (see Appendix I).

624 G Convolutions and Correlation Functions
S1
S2
x, ξ
Fig. G.1 Convolution scheme of two rectangular profiles as manifested by two slits S1 and S2 of
unequal size. Their respective transmission profiles are shown as full black and red dashed lines.
As slit S2 is shifted over slit S1 in x, ξ direction, the overlap (grey area) changes. The resulting
total transmission is shown as heavy red line (convolution)
Convolution and cross-correlation are well documented in mathematical tables as

well as in the web (often with illustrative animations, e.g. W EISSTEIN, 2011). Thus
we keep this brief recollection focused on the applications most often encountered
in AMO physics. Convolutions occur e.g. if a physical observable is analyzed and
detected that may assume a range of values described by a probability distribution
f1 (ξ ) as the variable ξ is changed. The measurement device too, will never be sensi-
tive at one and only one value of ξ . Rather the signal will be detected with a varying
detection probability f2 (ξ ). Hence, the detector is tuned over the region of interest
by shifting its detection efficiency through x. The resulting signal is described by
(G.3).
Two rectangular profiles are the simplest case – e.g. manifested as transmission
of light through two slits. This is shown for illustration of the principle in Fig. G.1,
starting with the situation in the leftmost cartoon with both slits separated from
each other where transmission is zero. The signal will increase (linearly) when S2
is shifted into +x-direction as soon as the areas of the slits begin to overlap. The
maximum is reached when the overlap is complete and stays constant as long as
the slits fully overlap. Further shift will reduce the signal again linearly. The overall
result is a capped triangular shape of the transmission profile (heavy red line in
Fig. G.1). It will be triangular if the two slits have equal width.
Typical applications are found in any kind of spectroscopy on atoms, molecules,
solids or in nuclear and elementary particle physics: the system absorbs, emits, re-
flects – photons, electrons, atoms or elementary particles – as a function of energy,
frequency or wavelength ξ , characteristic for the physics studied. A suitable detector
registers this signal with a specific detection probability which depends on ξ . This
may e.g. be controlled by the slit position and width of a spectrograph, the transmis-
sion curve of a frequency filter or particle energy analyzer. Recording a spectrum
implies changing ξ → ξ − x and thus shifting the transmission maximum of the
spectrograph – knowing that on the left and right of that maximum still some signal
is transmitted. The detector finally sums over all of this transmitted signal.
Convolution is also at work in nature when different processes may occur si-
multaneously in one system and overlay each other. A standard example is the
broadening of spectral lines emitted or absorbed by atoms and molecules. They
may e.g. move with a velocity described by the B OLTZMANN distribution and at the
same time undergo collisions. While the first effect leads to a significant, inhomo-
geneous spectral broadening due to the D OPPLER effect, collisions may also disturb
G.2 Correlation Functions and Degree of Coherence 625
the emission or absorption process and add to the broadening. The combination of
both effects is described by a convolution of the respective line profiles.
The physics involved in all these processes and examples will be discussed in
some detail in Sect. 5.1.1, and Chaps. 1, 2 in Vol. 2, and in other parts of these vol-
umes. In the present appendix we summarize a few useful mathematical expressions
which are needed to describe such measurements quantitatively. At the end one aims
of course at an intelligent de-convolution of the signal detected as a function of x,
i.e. one tries to extract the original profile f1 (ξ ) form the convoluted signal. This is
no trivial task unless the shapes of the two profiles involved are both well known.
Often one is content with just measuring the convolution and gleaning the width of
the profile f1 (ξ ) from known convolution formulas.
G.2 Correlation Functions and Degree of Coherence
In physics, the cross-correlation (G.3) – also called (first-order) correlation func-

tion – is often used to ‘correlate’ an observable at different points in space r and/or
time t . Typical observables are the electric field, or the intensity of an electromag-
netic wave. They may represent pulses (wave-packets), random sequences of pulses,
stationary signals (e.g. continuous light beams) or even more or less statistical noise.
Correlation functions describe the coherence of these observables in space and/or
time – in more colloquial terms one might say: the correlation function measures
traces of similarities over a distance in space and/or time.
The propagation of electromagnetic waves is described by its wave vector k and
angular frequency ω in the combination kr − ωt. Thus, with EA (t) = E(r, t) and
EB (t ) = E(r , t ) representing the field at two positions in space2 and time, one
may keep r constant, focus on the temporal coherence, and write the correlation
function in dependence of the time delay δ = t − t

1 Tav /2
G (δ) =
(1)
EA∗ (t)EB (t + δ) = EA∗ (t)EB (t + δ)dt. (G.4)
Tav −Tav /2
The angle brackets

. . . indicate averaging, the second equality giving one possible
recipe how to accomplish this averaging for the stationary case (e.g. for a CW light
beam or for continuous noise). Of course, integration has to be over a sufficiently
long time Tav so that all statistical short term fluctuations are smoothed out.
If EA and EB are square integrable functions, instead to average one has to inte-
grate over all times as in (G.3) and the 1/Tav factor becomes redundant. In normal-
ized form, the correlation function is called first-order degree of coherence:

EA∗ (t)EB (t + δ)
g (1) (δ) = . (G.5)
[
|EA (t)|2
|EB (t)|2 ]1/2
2 The further treatment is independent of whether EA and EB relate actually to two different fields
or represent the same field at different positions in space.
Correlation functions are e.g. used in state-of-the-art ultrafast science for the
determination of shape and duration of short laser pulses as to be detailed in Chap. 1,
Vol. 2. In such a measurement, the electric field amplitude EA (t) (or the intensity
∝ |EA (t)|2 ) of the pulse to be characterized is convoluted with a second light pulse
of well known profile EB (t) (or intensity ∝ |EB (t)|2 ). This is achieved by delaying
one pulse for a variable time δ in respect of the other. Both signals are multiplied
and integrated over a long time Tav . The signal is then recorded as a function of the
delay time δ and the result may finally be de-convoluted.
If EA (t) and EB (t) are identical (or just displaced in time) the first-order degree
of coherence (G.5) simply becomes the normalized autocorrelation function

E ∗ (t)E(t + δ)
E ∗ (t − δ)E(t)
g (1) (δ) = = = g (1) (−δ). (G.6)

|E(t)|2
|E(t)|2
The important symmetry with respect zero follows directly from the definition (G.4)
for A = B. If the shape of a pulse is already well known, it allows one to determine
directly the pulse duration (see below for special examples).
Note that here the 1/Tav factor cancels out in (G.5) and (G.6): these definitions
hold for CW fields as well as for a single pulses or a pulse sequence. In practice, the
averaging may not be that trivial, especially if E(t) is not given in closed analytical
form. For CW fields the average
. . . can be performed over times at a given po-
sition in space – or alternatively over the whole ensemble in space at a given fixed
time. One calls a system ergodic if the temporal average is equal to the average over
a representative ensemble – which is generally true for reasonable physical systems.
Usually the temporal average is more convenient to perform – while determining the
ensemble average (averaging over the whole space) would be a rather difficult task.
According to the ergodicity theorem,both averages are identical.
G.3 Gaussian Profile

In reality, experimental profiles are not just rectangular. To be specific, we start by
discussing the Gaussian profile – characteristic for a number of physical phenomena
and often also a good approximation for analyzer profiles. We write it in the form
most often used in atomic and laser physics:

2 1
fG (x; w, x0 ) = exp −2(x − x0 )2 /w 2 (G.7)

πw
√
with a FWHM of x = 2 ln 2w = 1.177w. (G.8)
We note that at x − x0 = w gives the distance at which fG has decreased to 1/e2 .

One easily verifies that fG (x; w, x0 ) is normalized according to (G.1). The mean
value
x and the variance σ 2 =
(x −
x)2 are given by

2 1 +∞ −2(x−x0 )2 /w2

x = xe dx = x0 , and (G.9)
π w −∞
G.4 Hyperbolic Secant 627

2 2 1 +∞ w2
(x − x0 )2 e−2(x−x0 )
2 /w 2
σ 2 = x −
x = dx = . (G.10)
πw −∞ 4
√
The standard deviation is thus σ = w/2 and the FWHM is 8 ln 2σ 1.2w.
An important case is the B OLTZMANN distribution for velocities in a gas. The
1D distribution in respect of the component vx , say, is given by

m mvx2
w(vx )dvx = exp − dvx (G.11)
2πkB T 2kB T
with the particle mass m, the absolute temperature T , and the B OLTZMANN con-
stant kB . The average velocity is
vx = 0, and the variance
vx2 = kB T /m.
D OPPLER broadening (Sect. 5.1.4) is a direct consequence of this Gaussian dis-
tribution. We recall from (5.21) its variance ωD 2 = ω2 k T /(mc2 ) with the angular
ba B
transition frequency ωba and the speed of light c.
Interestingly, the convolution (here identical to the cross-correlation) of two
Gaussian profiles with 1/e2 at x = w1 and w2 , respectively, is again a Gaussian
profile, with w 2 = w12 + w22 . One verifies easily (using e.g. SWP 5.5, 2005)
(fG fG )(x; w2 , x2 )
∞
2 1

= exp −2(ξ − x1 )2 /w12 × exp −2(ξ − x2 − x)2 /w22 dξ

π w1 w2 −∞

2 (x − (x1 − x2 ))2
= exp −2 , (G.12)
π(w12 + w22 ) w22 + w12
the convoluted FWHM thus being the geometric mean of both widths

x = 1.177w = 1.177 w12 + w22 = (x1 )2 + (x2 )2 . (G.13)
Thus, the autocorrelation function or the first-order degree of coherence (G.6) of a

Gaussian temporal profile with a FWHM t has a
√
FWHM: t auto = 2t. (G.14)
G.4 Hyperbolic Secant
The hyperbolic secant squared is another, often used line profile, in particular for
laser pulse intensities. Normalized according to (G.1) it is
sech2 [(x − x0 )/w] 1
fH (x; w, x0 ) = = (G.15)
2w 2w cosh [(x − x0 )/w]
2
2
1 2
= ,
2w e(x−x0 )/w + e−(x−x0 )/w
√
with a FWHM of x = −2 ln( 2 − 1) w = 1.763w. (G.16)

The convolution is a not completely trivial integral. For the autocorrelation function
one finds (properly normalized)
1 (x/w) cosh(x/w) − sinh(x/w)
(fH fH )(x; w) = (G.17)
w [sinh(x/w)]3
∼ 3 sech4 [x/(2.24445w)] sech2 [x/(1.5429w)]

=
4 × 2.24445w 2 × 1.5429w
all with a FWHM of x = 2.720w. (G.18)
The first equality is exact, the sech4 gives an excellent approximation, and the sech2
is still a good approximation for small |x| ≤ 1.7; in the far wings, however, it is
somewhat too high.
G.5 LORENTZ Profile
Another profile often encountered is the L ORENTZ profile, describing e.g. the natu-
ral line profile or collision broadening (see Sects. 5.1.1 and 5.1.3, respectively). We
write the L ORENTZ profile
2 γ 2 /4
fL (x; γ , x0 ) = (G.19)
γ π (x − x0 )2 + γ 2 /4
with a FWHM x = γ , (G.20)
again properly normalized according to (G.1). The L ORENTZ profile is a partic-

ularly wide profile (see Fig. 5.5) and its variance
x 2 obviously diverges since
fL (x; γ , x0 ) → 1/x 2 for large x, while its mean value is
x = x0 .
The convolution of one L ORENTZ profile with another leads again to a L ORENTZ
profile (for a proof see e.g. Appendix I.4.5):
2 γ 2 /4
(fL fL )(x; γ2 , x2 ) = (G.21)
γ π (x − (x1 − x2 ))2 + γ 2 /4
with the FWHM of the convolution x = γ = γ1 + γ2 .
G.6 VOIGT Profile
Convolution of a L ORENTZ with a G AUSS profile is required e.g. for optical line
shapes of atoms or molecules in the gas phase if D OPPLER broadening and collision
broadening are on the same order of magnitude (or at low temperatures D OPPLER
and natural linewidth). This so called VOIGT profile
+∞
e−2ξ /w
2 2
2 1 γ
fV (x; σ, γ ) = (fG fL )(x; γ , 0) = dξ, (G.22)
π w 2π −∞ (ξ − x)2 + γ 2 /4
is an integral which cannot be evaluated by standard integration formulas. With

some advanced functions this may, however, be achieved. Extended literature exists
on the subject. We essentially follow NIST-DLMF (2013) and W IKIPEDIA CON -
TRIBUTORS (2014). Properly normalized according to (G.1) and with the definitions
for w and γ used above, the VOIGT function can be expressed as

2 Re(exp(−z2 ) erfc(−iz))
fV (x; w, γ ) = (G.23)
π w
√
2
with z = (x + iγ /2) (G.24)
w
where exp(−z2 ) erfc(−iz) is the complex error function (also FADEEVA function).
The complementary error function erfc(x) = 1 − erf(x) is usually implemented in
modern symbolic mathematics programmes (we use SWP 5.5, 2005). Even an ap-
proximate linewidth (FWHM) for the VOIGT profile is found in the literature as

ωV = 0.5346ωL + 0.2166(ωL )2 + (ωD )2 , (G.25)
supposed to be accurate to within 0.02 %, where ωL and ωD are the FWHM
of L ORENTZ and D OPPLER profile, respectively. One example of this convoluted
D OPPLER and collision profile for ωL = ωD is shown in Fig. 5.5. In this case
the formula gives ωV = 1.638ωL .
AMO: ‘Atomic, molecular and optical’, physics.

CW: ‘Continuous wave’, (as opposed to pulsed) light beam, laser radiation etc.
FWHM: ‘Full width at half maximum’.
NIST: ‘National institute of standards and technology’, located at Gaithersburg
(MD) and Boulder (CO), USA. http://www.nist.gov/index.html.
References
NIST-DLMF: 2013. ‘Digital library of mathematical functions: §7.19 Voigt functions’, NIST.
http://dlmf.nist.gov/7.19, accessed: 9 Jan 2014.
SWP 5.5: 2005. ‘Scientific work place’, Poulsbo, WA 98370-7370, USA: MacKichan Software,
Inc. http://www.mackichan.com/, accessed: 9 Jan 2014.
W EISSTEIN, E. W.: 2011. ‘Convolution’, Wolfram Research, Inc., Champaign, IL, USA. http://
mathworld.wolfram.com/Convolution.html, accessed: 9 Jan 2014.
W IKIPEDIA CONTRIBUTORS: 2014. ‘Voigt profile’, Wikipedia, The Free Encyclopedia. http://en.
wikipedia.org/wiki/Voigt_profile, accessed: 9 Jan 2014.
Vector Potential, Dipole Approximation,
Oscillator Strength H
H.1 Interaction of the Field of an Electromagnetic Wave with

an Electron
In view of its clearness and compactness we use in this book – apart from a few ex-
ceptions – in general the dipole length approximation for describing the interaction
of electromagnetic waves with atoms and molecules. It is thus appropriate to justify
this approach in some detail. In addition, we shall provide the basis for some useful
concepts related to the dipole approximation.
H.1.1 Vector Potential
In the quantum mechanically correct formulation for the interaction of an electro-

magnetic field with charged particles one replaces the momentum operator p=
−i∇ of the particle (charge q) by p field =
p − qA, where A = A(r, t) is the vector
potential of the field. The Hamiltonian of an electron in the field thus becomes

p 2field 1
=
H + V (r) = p + eA)2 + V (r)
( (H.1)
2me 2me
p2 p·A
e e2 2
= + V (r) + + A (H.2)
2me me 2me
where the so called C OULOMB gauge of the field has been used:
∇ · A = 0. (H.3)
For simplicity we have restricted the discussion to a single active electron. One
easily generalizes (H.2) to multi-electron systems by replacing momentum p and
position vector r with p i and r i , respectively, for each electron i, and summing
over all electrons.

632 H Vector Potential, Dipole Approximation, Oscillator Strength
The vector potential A relates to the electric and magnetic field vectors
∂
E(r, t) = − A(r, t) + ∇Vext and B(r, t) = ∇ × A(r, t) (H.4)
∂t
with Vext (r, t) describing an additional, external potential. If such a field is present,
one has to add Vext to V (r) in (H.1) and (H.2). Not included in this description are
of course all interactions related to the electron spin which follow from the D IRAC
equation, including spin-orbit interaction, as briefly discussed in Chap. 6.
In vacuum, we write the vector potential, electric field, and magnetic field for a
plane electromagnetic wave as:
A0 i(kr−ωt)
A(r, t) = ee + e∗ e−i(kr−ωt) = A0 e cos(kr − ωt) (H.5)
2
iE0 i(kr−ωt)
E(r, t) = ee − e∗ e−i(kr−ωt) = E0 e sin(kr − ωt) (H.6)
2
iB0 k i(kr−ωt) k
B(r, t) = × ee − e∗ e−i(kr−ωt) = B0 × e sin(kr − ωt). (H.7)
2 k k
The relations among the amplitudes are derived from (H.4)
ω
E0 = ωA0 , B0 = kA0 = A0 , and B0 = E0 /c. (H.8)
c
H.1.2 Intensity
The P OINTING vector

E×B
S =E×H =
μ0
gives the energy flux. With E ⊥ B and ε0 μ0 = 1/c2 we obtain its absolute value,
called intensity:
ε0 c[E0 (r, t)]2 −iωt 2
If (r, t) = |S| = ε0 c|E|2 = ee − e∗ eiωt (H.9)
4
ε0 c[E0 (r, t)]
2
= 1 + sin(2β) cos(2ωt) . (H.10)

2
Here we have inserted for e the general unit polarization vector (4.15) with the
ellipticity angle β. Obviously, depending on β, the intensity If (r, t) may oscillate
fast (with 2ω) in position space and time, as emphasized by the index ‘f’. However,
independent of β one obtains the cycle averaged intensity
2 2
I (r, t) = If (r, t) = ε0 c E(r, t) = ε0 cω2 A(r, t)
ε0 c
2 ε0 cω2
2 c
2 (H.11)
= E0 (r, t) = A0 (r, t) = B0 (r, t) .
2 2 2μ0
H.1 Interaction of the Field of an Electromagnetic Wave with an Electron 633
In principle, the amplitude E0 (r, t) (and A0 and B0 ) as well as the averaged intensity
I (r, t) may still depend slowly on time t and position r. This is called SVE.1 More
about cycle averaged intensities is discussed in Sect. 1.3.1, Vol. 2. The electric field
is measured in units [E0 ] = V m−1 , the intensity in [I ] = W m−2 .
Note that all field quantities used here represent quasi-monochromatic waves:
their bandwidth is assumed to be much narrower than any atomic or molecular ab-
sorption line studied. The transition to a continuous spectrum is made by replacing
I → I˜(ω)dω, where the spectral intensity distribution I˜(ω) (or the spectral energy
density ũ(ω) = I˜(ω)/c) refer to the unit
& of angular frequency interval. Finally, one
has to integrate over all frequencies: . . . dω.
H.1.3 Static Magnetic Field
For a static, homogeneous external magnetic field B one derives the vector potential
by inverting (H.4):
1 1
A = − r × B = B × r. (H.12)
2 2
This may be verified by inserting this expression into (H.4).2
For such a constant B field the Hamilton operator (H.2) becomes
=
H
p2
+ V (r) +
e
L·B +
e 2 A2
, (H.13)
2me 2me 2me
where for the third term we have used the identity (B × r) · p = B · (r ×

p ) for
the scalar triple product and the definition of angular momentum L=r × p . This
term corresponds exactly to (6.29) with (6.27), i.e. we have derived here correctly
the interaction potential of an external magnetic field with the magnetic moment of
the orbital angular momentum. A heuristic derivation is given in Chaps. 1 and 6.
The final term in (H.13) represents a (usually) small correction
e 2 A2 e2 2 2
= r B sin θ, (H.14)
2me 8me
1 The SVE approximation demands that |∂E

0 /∂t| ωc E0 as well as |∂E0 /∂z| E0 /λc etc. Then,
second order derivatives may be neglected in the general wave equation.
2 The triple vector product is expanded as

1 1
∇ × A = ∇ × − r × B = − [B · ∇r − r · ∇B + r∇ · B − B∇ · r].
2 2
The first two terms are directional gradients. B · ∇r = B and for a homogeneous B field
r · ∇B = 0. The third term also disappears since ∇ · B = div B ≡ 0. With div r = 3 the forth
term = −3B. Finally, the whole right hand side gives −(1/2)(B − 3B) = B, q.e.d.
where θ is the angle between the external B field and the position vector r of the
electron in the atom. We estimate for, say, 30 T and r = a0 a maximum value of ca.
5 × 10−8 eV. Thus, in spectroscopy this term only plays a role if extreme accuracy
is asked for or very high magnetic fields and very large orbital radii are involved
(i.e. high lying RYDBERG states). On the other hand, it is this very term which is
responsible for all diamagnetism of matter.
H.1.4 Relation Between Matrix Elements of p and r
For the following considerations we derive an important relation between the matrix
elements of momentum and position. For electrons i and j the standard commuta-
tion rules for canonically conjugated observables (momentum and position) hold:
[xi , p
yj ] = 0 and [xi , p
xj ] = iδij , etc. (H.15)
With these and the identity

a,
a,
b2 = [ b]
b + a,
b[ b] (H.16)
we can write
] = i p
[xi , H xi and [r, H ] = i p, (H.17)
me me

where r = r i and p= p i . Thus, for the matrix elements of
p between eigen-
states |a and |b of the Hamiltonian we derive
me ]|a = me (Wa − Wb )
b|r|a.

b|
p |a =
b|[r, H (H.18)
i i
With (Wa − Wb )/ = −Wba / = −ωba the sought-after relation between the matrix
elements of
p and r is:

b|
p |a = ime ωba
b|r|a. (H.19)
H.1.5 Ponderomotive Potential
Before actually evaluating the matrix elements of the interaction in the Hamiltonian
(H.2) in detail, we have a second look at the term proportional to A2 , now for an
atom or molecule in an electromagnetic wave. Clearly, this term is a time dependent
additional energy in the Hamiltonian. By averaging A2 over one period we obtain
with (H.11) an estimate for its dependence on intensity I :
e2
A2 e2 I
Up = = . (H.20)
2me 2ε0 cme ω2
H.1 Interaction of the Field of an Electromagnetic Wave with an Electron 635
This is identical to the expression (8.139) discussed in Sect. 8.5.1 for the pondero-
motive potential Up . There, a completely classical picture of an electron oscillating
in the electric field of the wave is used to ‘derive’ it.
In respect of standard laser spectroscopy, the ponderomotive potential is usually
negligible. As described in Sect. 8.5.1, however, it leads to very interesting phe-
nomena if the objects studied are exposed to very intense electromagnetic radiation
which can be generated without difficulties by today’s short pulse lasers.
H.1.6 Series Expansion of the Perturbation and the Dipole

Approximation
now discuss the term proportional to A ·

p in (H.2) which is responsible for electro-
magnetically induced transitions. With (H.5) it is
e A0
(
U p , r, t) = p · eei(kr−ωt) + e∗ e−i(kr−ωt)

me 2
eE0 −iωt
=
De − D∗ e+iωt . (H.21)
2
We abbreviate the transition operator
D
eik·r −ieik·r

D=
p·e= ∇·e (H.22)
ωme ωme
(with the dimension L) and the amplitude

eE0 = eωA0 = ecB0 = e 2I /(cε0 ) (H.23)
(with the dimension of a force MLT−2 ). For electromagnetic waves in the IR, VIS,
UV, and VUV spectral range the wavelength is usually very large compared to the
objects studied. We thus can assume k · r 1 and expand the exponential function
in (H.22):
1

D= (1 + ik · r + · · · )
p · e. (H.24)
ωme
In the electric dipole approximation (short: dipole approximation) only the first
term is taken into account and one speaks of E1 transitions. Thus, the dipole transi-
tion matrix elements of D between two eigenstates |a and |b is:
1

Dab =
a|
p |b · e = −i a|∇|b · e = i
a|r|b · e. (H.25)
ωba me ωba me
For the last equality we have made use of (H.19). Strictly mathematical, both forms
of
Dab are completely equivalent – if the wave functions used are exact solutions of
the unperturbed Hamiltonian. However, since we usually know the wave functions
only approximatively (except for some special cases such as the H atom) both for-
mulas (H.26) and (H.27) lead to slightly different results. Both variants are used in
the literature: they are called dipole velocity approximation (since
v = p /me ), and
the dipole length approximation, respectively.
The matrix elements of the interaction potential (H.21) are thus

i e 2I (ω)
ab (t) =
a|U
U (r, t)|b = −
a|∇|b · ee−iωt + e∗ e+iωt (H.26)
2 ωme cε0
or alternatively in dipole length approximation

U (r, t)|b = i E0
a|er|b · ee−iωt − e∗ e+iωt .
ab (t) =
a|U (H.27)
2
The latter form is identical to that obtained from the heuristic considerations pre-
sented in Sect. 4.3.4.
All expressions above refer to a single active electron which is excited or de-
excited in an external electromagnetic field. For larger atoms and molecules more
than one electron (in principle all) can participate in the interaction – even simul-
taneously. Such events typically lead to interesting phenomena (see e.g. autoioniza-
tion, Sect. 7.6). Thus, in general one has to sum the respective interaction potentials
for all electrons. The transition operator (H.22) will then read
N N
1 ik·r i −i ik·r i

D= e
pi · e = e ∇ i · e. (H.28)
ωme ωme
i=1 i=1
Specifically, in dipole approximation for a multi-electron system the transition ma-

trix element (H.25) has to be replaced by
N N

Dab = −i
a| ∇ i |b · e = i
a| r i |b · e. (H.29)
ωba me
i=1 i=1
The first and second equality refer to the dipole velocity and dipole length form
of the transition operator, respectively. They are identical if (and only if) the wave
functions are exact. The sum has to be carried out in principle over all electrons i,
with N being the total number of electrons in the system.
H.2 Line Strength and Oscillator Strength

H.2.1 Definitions
Several, slightly differing, quantities are used in the literature to characterize the
overall strength of a dipole transition between levels a and b with angular mo-
mentum quantum numbers ja ma and jb mb , and degeneracies ga = 2ja + 1 and
H.2 Line Strength and Oscillator Strength 637
gb = 2jb + 1, respectively. In principle, j may refer to the orbital (L) or to the to-
tal angular momentum (J ), whichever is appropriate. Note that we abbreviate the
quantum numbers γa ja ma := a, but we also use a and b for designating the respec-
tive energy levels – as long as no confusion can arise.
We essentially3 follow C ONDON and S HORTLEY (1951) and define the line
strength symmetric in respect of initial and final energy levels and as a sum over
all polarizations:

S(jb ja ) ≡ S(ja jb ) := |r ba |2 ≡
γb jb mb |r|γa ja ma 2
mb ma mb ma

(H.30)
=
b|x|a 2 +
b|y|a 2 +
b|z|a 2 .
mb ma
The dimension of the line strength is L2 .

In spherical coordinates (see 4.75) this may be written even more explicitly:

S(jb ja ) =
γb jb mb |rq |γa ja ma 2 ≡ S(ja jb )
mb ma q
2 (H.31)
=
γb |r|γa
jb mb |C1q |ja ma 2 .
q mb ma
Using the W IGNER -E CKART theorem in the form (4.82) and the orthogonality re-
lations of the 3j symbols (B.42) we obtain the compact relations:4
2
S(jb ja ) = (2jb + 1)
γb |r|γa
jb C1 ja 2
2 (H.32)
= (2ja + 1)
γa |r|γb
ja C1 jb 2 ≡ S(ja jb ).
If LS coupling is appropriate, one may recouple the reduced matrix elements
Ja La SC1 Jb Lb S2 using (C.46). Exploiting the orthogonality relation (B.67) for
the 6j symbols one obtains the relation
S(Jb Ja ) S(Lb La )
, (H.33)
2Jb + 1 2Lb + 1
Ja
where the equality sign holds in so far as the radial matrix element does not depend
on the individual fine structure levels J but only on the orbital quantum numbers L
and n – which is a good approximation for light atoms.
3 The line strength S CS (j j ) used by C ONDON and S HORTLEY (1951) is related by S CS (j j ) =

b a b a
eS(jb ja ) to the quantity used here – which leads to more compact formulas for the A and B
(opt)
coefficients and for the oscillator strength fba .
4 Notethat a factor 3 arising here from the sum over all polarizations q is compensated by a factor
1/(2 × 1 + 1) = 1/3 from the orthogonality relations of the C LEBSCH -G ORDAN coefficients when
summing over ma and mb .
Complementary to the line strength, which is symmetric and has a dimension L2 ,

the so called oscillator strength f(opt) (e) is defined asymmetrically and dimension-
less for a given polarization with unit vector e. We first define it for a specific tran-
sition from one initial substate |a = |ja ma to one final substate |b = |jb mb :

2Wba 2Wba r ba 2
(opt)
fjb mb ←ja ma (e) = | |2
= · e (H.34)
Eh a02
D ba
E h a0 .
Here Dba is the dipole transition matrix element (H.29). In the second equality we
use explicitly the dipole length form for a single electron system, with r ba as de-
fined by (4.79). The oscillator strength is thus proportional to the transition proba-
bility (4.65). And since it is also proportional to the absorbed (or emitted) photon
energy Wb − Wa = Wba = ωba , its value is positive for absorption and negative for
emission.
For the particular case of linear polarization with elin z this gives a simple ex-
pression for the oscillator strength:

(opt) Wba zba 2 me ωba
fjb mb ←ja ma =2 =2 |zba |2 . (H.35)
E h a0
It may be further evaluated with (4.75) and the W IGNER -E CKART theorem in the
form (4.82):
2
|zba |2 =
γb jb mb |r0 |γa ja ma
2 (H.36)
2 ja 1 jb
= (2jb + 1)
γb |r|γa
jb C1 ja 2 .
−ma 0 mb
Note that this becomes zero for mb = ma .

In an experiment one typically averages over all initial substates |ja ma and sums
over all final substates |jb mb . If the initial level is populated
isotropically one ob-
tains for an arbitrary unit polarization vector e = q aq eq for the transition be-
tween from level jb to level ja with (H.34) and (4.93)

(opt) 1 (opt) 2 Wba r ba 2
fjb ja = f (e) = · e (H.37)
ga m m jb mb ←ja ma ga E h m m a 0
a b a b
1 2
2 Wba
1

=
γb jb mb |rq |γa ja ma e∗q · aq e q
ga E h m m

a b q=−1 q =−1
2 Wba 2 2
1
= |aq |2
γb |r|γa
jb mb |C1q |ja ma . (H.38)
ga E h m m
a b q=−1
H.2 Line Strength and Oscillator Strength 639

Using (4.82), the orthogonality relation (B.42) for the 3j symbols, and q |aq |2 = 1
(unit vector e) the sums can be carried out:
2
Wba gb r
1
1
(opt)
fjb ja =2
γ | |γ
jb C1 ja 2 |aq |2 (H.39)
E h ga
b a
a0 3
q=−1
2
(opt) 2 Wba gb r

fjb ja =
γ b | |γ a
jb C1 ja .
2
(H.40)
3 E h ga a0
Finally by comparing this with (H.32) we obtain the expression
(opt) 2 Wba S(jb ja ) 2me ωba S(jb ja )

fjb ja = = (H.41)
3ga Eh a02 3 ga
as used in Sect. 5.2.2. We note here one very important result:
The averaged oscillator strength for an isotropically populated initial level –

and hence the probability for absorption or induced emission – is independent
of the polarization.
Thus, we also may simply average (H.35)

(opt) 2 Wba zba 2 2me ωba 1
fjb ja = = |zba |2 (H.42)
ga E h m a 0 ga m
a a
where we have exploited that here q = 0, and thus only contributions from ma = mb
arise. For an initial singly degenerate ns state (H.42) is reduced to (H.35). Equivalent
expressions are derived from (H.41) with (H.30) and the dipole moment D = −er:
2me ωba 2

γb jb mb |r|γa ja ma
(opt)
fjb ja = (H.43)
3ga m m
2
a b
2
2 Wba r
8π 2 me Wba
=
γ j m
b b b | |γ a a a =
j m |D ba |2 .
3ga Eh m m a0 3ga h2 e2 m m
a b a b
(H.44)
Note the factor 3 in the denominator in comparison to (H.42), compensating for the
equal contributions from the components of |r|2 = |x|2 + |y|2 + |z|2 .
H.2.2 THOMAS-REICHE-KUHN Sum Rule
We sum the oscillator strength according to (H.35) over all existing final states |b =
|γb jb mb and rewrite the expression suitably:
(opt)
2me ωba 2me ωba
fjb mb ←ja ma = |zba |2 =
a|z|b
b|z|a (H.45)

b b b
1
= ime ωba
a|z|b
b|z|a − ime ωab
a|z|b
b|z|a .
i
b
Now we apply (H.19) and obtain

(opt) 1
fjb mb ←ja ma =
a|z|b
b|pz |a −
a|pz |b
b|z|a
i
b b
(H.46)
1

a|zpz − pz z|a
=
a|zpz |a −
a|pz z|a = = 1,
i i

where we have exploited completeness 1 = b |b
b|. The last step realizes the
commutation rules (H.15) and normalization
a|a = 1.
We note that this derivation does not depend on the specific initial substate |a =
|ja ma since summation is always over all final states |b. Hence, (H.46) is also valid
(opt)
for the average oscillator strength fjb ja . Thus, we have derived the very important
T HOMAS -R EICHE -K UHN sum rule:
(opt)
fjb ja = 1. (H.47)
b
The oscillator strength is often used in atomic and molecular physics to characterize
dipole transitions. It allows one to compare the strength of different transitions in
(opt)
different atoms or molecules. For systems with one active electron fjb ja ≤ 1 strictly
holds, the classical reference being an oscillating electron which has an oscillator
strength = 1.
For systems with Ne active electrons one has to replace in (H.45) the single
e (i)
electron coordinate z by N i=1 z and obtains the sum rule:
(opt)
fjb ja = Ne . (H.48)
b
Finally, we point out that the summation just discussed must include the ion-
ization continuum if the basis is to be complete. In this context, continuum states
are usually normalized in the energy scale (see Appendix J). Correspondingly one
defines the optical oscillator strength density (OOSD), df(opt) /d, with the dimen-
sion Enrg−1 , where is the energy of the emitted electron in the continuum. Thus,
(H.48) includes summation over discrete states and integration for energies beyond
the ionization potential WI :

discrete ∞ (opt)
dfja
(opt) (opt)
fjb ja → fjb ja + d. (H.49)
WI d
b b
Obviously for high energies, limW →∞ (df(opt) /d) = 0 must hold.

E1: ‘Electric dipole’, transitions induced by the interaction of an electric dipole

with the electric field component of electromagnetic radiation.
IR: ‘Infrared’, spectral range of electromagnetic radiation. Wavelengths between
760 nm and 1 mm according to ISO 21348 (2007).
OOSD: ‘Optical oscillator strength density’, characterizes the strength of photoion-
ization per energy interval (see Sect. 5.5.1).
SVE: ‘Slowly varying envelope’, approximation for electromagnetic waves (see
Sect. 1.2.1, specifically Eq. (1.38), Vol. 2).
UV: ‘Ultraviolet’, spectral range of electromagnetic radiation. Wavelengths be-
tween 100 nm and 400 nm according to ISO 21348 (2007).
VIS: ‘Visible’, spectral range of electromagnetic radiation. Wavelengths between
380 nm and 760 nm according to ISO 21348 (2007).
VUV: ‘Vacuum ultraviolet’, spectral range of electromagentic radiation. part of the
UV spectral range. Wavelengths between 10 nm and 200 nm according to ISO
21348 (2007).
References
ISO 21348: 2007. ‘Space environment (natural and artificial) – process for determining solar
irradiances’. International Organization for Standardization, Geneva, Switzerland.
FOURIER Transforms and Spectral Distributions
of Light I
I.1 Short Summary on FOURIER Transforms

The F OURIER transform (FT) is a mathematical tool widely used in physics and
engineering. We collect here the most important definitions and relationships and
give a few practical examples, focussing on the description of short light pulses.
F OURIER transforms are based on the complex version of the F OURIER integral
(here without proof):
∞ ∞
1
X(t) = eiωt dω X(τ )e−iωτ dτ (I.1)
2π −∞ −∞
∞ ∞
or = e 2πiνt
dν X(τ )e−2πiντ dτ.
−∞ −∞
Various, slightly different notations can be found in the literature. We use the stan-
dard notations of modern physics with the F OURIER transform1
∞

(
X(ω) = F X(t) = X(t)e−iωt dt (I.2)
−∞
of the time dependent function X(t). Conversely, X(t) is recovered by the inverse
F OURIER transform
∞

1
(
X(t) = F −1 X(ω) = (
X(ω)e iωt
dω. (I.3)
2π −∞
The complex conjugate of the F OURIER transform of X(t) is

∞
(∗
X (ω) = X ∗ (t)eiωt dt, (I.4)
−∞
1 In
√
other notations the factor 1/2π is applied symmetrically as 1/2π , or completely avoided by
using frequency ν instead of angular frequency ω = 2πν.

644 I FOURIER Transforms and Spectral Distributions of Light
and correspondingly
∞
1 (∗ (ω)e−iωt dt.
X ∗ (t) = X (I.5)
2π −∞
By rewriting (I.1) as
∞ ∞
1
X(t) = X(τ ) e iω(t−τ )
dω dτ
−∞ 2π −∞
one identifies the expression in square brackets as the D IRAC delta function:
∞

1
δ(t − τ ) = F −1 e−iωτ = eiω(t−τ ) dω (I.6)
2π −∞
∞
1 iωc t
1
and equivalently δ(ωc − ω) = F e = e−i(ω−ωc )t dt. (I.7)
2π 2π −∞
With this, one verifies the important relationship

∞
∞ 2
X(t) 2 dt = 1 (
X(ω) dω, (I.8)
−∞ 2π −∞
called P LANCHEREL’s theorem (sometimes PARCEVAL’s theorem – which actually

refers to F OURIER series – or R AYLEIGH’s theory). To proof it, one just has to insert
(I.3) and (I.2), rearrange the integrations and recover the D IRAC delta function. We
leave it to the reader to work out the details. As we shall see below, for electromag-
netic radiation P LANCHEREL’s theorem essentially states energy conservation.
In the context of describing short pulses of light, we note a very useful relation
for the F OURIER transform of an oscillation around a carrier frequency ωc with an
envelope function X(t): With X(ω)( = F[X(t)] we can write
∞ ∞
1 ( 1 iωc t ( − ωc )ei(ω−ωc )t dω
X(t)e iωc t
=e iωc t
X(ω)e iωt
dω ≡ e X(ω
2π −∞ 2π −∞
∞
1
= X(ω ( − ωc ) .
( − ωc )eiωt dω = F −1 X(ω (I.9)
2π −∞
Thus, the carrier frequency just shifts the F OURIER transform F[X(t) exp(iωc t)]
towards positive frequencies in respect of F[X(t)]. This formally also resolves the
problem one might envisage with negative frequencies in the spectral distribution
(
X(ω): since for any physically relevant distribution with a FWHM= γ one expects
ωc γ , there will be no contributions from negative frequencies in (I.2). An ana-
logue relation applies to a shift in time.
Another set of useful relations concerns F OURIER transforms of convolutions
(see Appendix G). The proof is similar to that for P LANCHEREL’s theorem.
I.1 Short Summary on FOURIER Transforms 645
1. The convolution theorem states that the F OURIER transform of a convolution of

(
two functions X(t) and Y (t) is the product of their F OURIER transforms X(ω)
(
and Y (ω):

F (X ∗ Y )(t) = F X(t) F Y (t) = X(ω) ( Y ((ω). (I.10)

This is proven as follows:

∞ ∞

−iωt

F (X ∗ Y )(t) = X t Y t − t dt e dt
−∞ −∞
∞ ∞
−iωt
= X t e dt Y t − t e−iω(t−t ) dt
−∞ −∞
∞ ∞

= X t e−iωt dt Y t e−iωt dt .
−∞ −∞
2. The F OURIER transform of a product of two functions is the convolution of their

F OURIER transforms:

1

1 ( (
F X(t)Y (t) = F X(t) ∗ F Y (t) = (X ∗ Y )(ω). (I.11)
2π 2π
And the proof for this relation is only slightly more complex, involving the
D IRAC delta function:

F X(t)Y (t)
∞ ∞ ∞
1 iω t 1 iω t −iωt
= (
X ω e dω (
Y ω e dω e dt
−∞ 2π −∞ 2π −∞
∞ ∞
1 iω t
= (
X ω e dω
−∞ 2π −∞
∞
1
× ( ω − ω ei(ω −ω )t dω e−iωt dt
Y
2π −∞
∞ ∞ ∞
1 1
= ( ω Y
X ( ω − ω dω dω ei(ω −ω)t dt
2π 2π −∞ −∞ −∞
∞ ∞
1
= δ ω − ω X (ω Y ( ω − ω dω dω
2π −∞ −∞
∞
1
= ( ω Y
X ( ω − ω dω .
2π −∞
The inverse relations of course also hold:

F −1 (X (∗Y()(ω) = 2πX(t)Y (t) and (I.12)

( Y
F −1 X(ω) ((ω) = (X ∗ Y )(t). (I.13)
3. In analogy to the convolution theorems, the cross-correlation theorems

∗
F (X Y )(t) = F X(t) F Y (t) = X (∗ (ω)Y

((ω) and (I.14)

1

1 ( (
F X ∗ (t)Y (t) = F X(t) F Y (t) = (X Y )(ω) (I.15)
2π 2π
hold, as well as their inverse relations.
From these expressions follows directly a very important relationship between

F OURIER transform and autocorrelation function, the W IENER -K HINCHIN theo-
rem:
∞

−1 (
2
F
X(ω) = X ∗ (τ )X(τ + t)dτ or (I.16)
−∞

2 ∞
(X(ω) = F X ∗ (τ )X(τ + t)dτ . (I.17)
−∞
I.2 How Electromagnetic Fields are Written

With these tools at our command we want to describe wave-packets, i.e. short, co-
herent light pulses. At this point, we emphasize again that real electromagnetic fields
are real observables, i.e. measurable quantities! One often finds in the literature that
electromagnetic wave fields are ‘for simplicity’ written in complex form. However,
albeit the greater mathematical simplicity of the complex form is indeed attractive,
one may easily overlook some important aspects by a too naive use of the complex
form – as we have documented in Chap. 4, when describing absorption and induced
emission of light in quantum mechanical terms.
Thus, following (4.1) we write the electric field vector E(r, t) of a wave-packet
as a real quantity, explicitly using its two conjugate complex terms. For simplicity
of writing we ignore here the r dependence2 in E0 (r, t) and keep the position in
space constant kr = 0:
1
E(t) = E0 (t) ee−i(ωc t−φc ) + e∗ ei(ωc t−φc ) (I.18)

2
1
∗
≡ eE − (t) + e∗ E + (t) with E + (t) = E0 (t)ei(ωc t−φc ) = E − (t) .
2
In the spirit of the so called SVE approximation (see footnote 1 in Appendix H), we
have introduced here E0 (t), the time dependent envelope of the field – now a real
function depending on time. The phase φc may also depend on time and position (see
e.g. (1.46) in Vol. 2). It allows to specify the relative phase of the carrier oscillation
±ωc t → ∓k c r ± ωc t .
2 Where necessary, we shall simply reintroduce the wave vector by replacing
Similarly, we keep the r dependence of the envelope in the back of our mind and set E ± (t) →
E ± (r, t) when required.
I.2 How Electromagnetic Fields are Written 647
in respect of the envelope E0 (t) as illustrated in Fig. 1.24 in Vol. 2. In nonlinear

optics and ultrafast science it plays a significant role for a variety of processes. To
make things not too complicated here, we assume in the following φc to be constant
with time, and we shall focus on the E + (r, t) term, so that we can still exploit the
advantages of complex arithmetic.
Within the SVE approximation we are interested in the temporal dependence of
the intensity of the electromagnetic field. According to (H.11), ignoring the position
dependence, the average intensity is
ε0 c
2 ε0 c −
I (t) = If (t) = E0 (t) = E (t)E + (t). (I.19)
2 2
Here
If (t) indicates cycle averaging over fast oscillations. For reference we also
communicate the cycle average energy density of the field

If (t) ε0 −
uf (t) = = E (t)E + (t). (I.20)
c 2
The electric field of a light pulse may be expressed as inverse F OURIER trans-
form, i.e. as a linear superposition of oscillators with frequencies ω around the car-
rier frequency ωc in a bandwidth δω ωc :
∞
1 (
E0 (t) = E(ω)e iωt
dω. (I.21)
2π −∞
To explicitly show the carrier frequency ωc and phase φc , we apply (I.9):
∗
E + (t) = E0 (t)ei(ωc t−φc ) = E − (t)
∞
e−iφc ∞ ( 1 (+ (ω)eiωt dω.
= E(ω − ωc )eiωt dω = E (I.22)
2π −∞ 2π −∞
Conversely, the F OURIER transform of the field envelope is
∞
(
E(ω) = E0 (t)e−iωt dt, (I.23)
−∞
or alternatively one may write3

−
(+ (ω) = E(ω
E ( − ωc )e−iφc = E ( (−ω) ∗
∞ ∞
= E + (t)e−iωt dt = e−iφc E0 (t)ei(ωc −ω)t dt. (I.24)
−∞ −∞
3 Even (+ (ω))∗ = E
though (E + (t))∗ = E − (t), note that (E (− (ω), since
∞ ∗ ∞
+ ∗ + ∗ iωt
( (ω) =
E E + (t)e−iωt dt = E (t) e dt
−∞ −∞
∞
= (− (−ω).
E − (t)eiωt dt = E
−∞
(
Note that in this terminology E0 (t) is a real quantity. E(ω) will also be real if and
only if E0 (t) is symmetric around its maximum, while E (+ (ω) is usually complex.
However, with these definitions E (+ (ω) typically has a pronounced resonance at
ω > 0 so that contributions from negative frequencies to the inverse FT (I.22) can
safely be neglected. In other words: artificial truncations of the limits of integrals
are not needed, since anyhow only positive frequencies contribute when working
with E(+ (ω). These relationships will be illustrated below for specific examples.
I.3 The Intensity Spectrum
If one inserts E ± (t) according to (I.22) into expression (I.19) for the cycle averaged
intensity and integrates over all times, one recovers P LANCHEREL’s theorem (I.8)
∞ ∞ ∞
ε0 c 1 + 2
I (t)dt =
E (ω) dω = I˜(ω)dω = F, (I.25)
−∞ 2 2π −∞ −∞
leading to the fluence F (i.e. the total pulse energy Wtot per unit area). With the
second equality we have defined the spectral intensity distribution:
ε0 c (+ 2 ε0 c ( 2
I˜(ω) = E (ω) = E(ω − ωc ) . (I.26)
4π 4π
The assumption that this indeed describes the spectrum of the radiation is by
no means as trivial as commonly assumed. Note, that this expression is not the
F OURIER transform of the intensity I (t)!
One may, however, rationalize this definition by remembering how optical (or
other) spectra of electromagnetic radiation are measured: Assume e.g. an interfero-
metric measurement (FABRY-P ÉROT interferometer, diffraction grating etc.), where
the signal S is generated by superposition of two (or many) amplitudes. A typical
interference pattern emerges from, say two wave fields E + (t) and E + (t + δ), which
have traversed different optical path length cδ (corresponding to a delay time δ). The
signal is then

S ∝ E − (t) + E − (t + δ) E + (t) + E + (t + δ) (I.27)

= 2I0 + 2 Re E − (t + δ)E + (t) ,
and only the interference term [in square brackets] is relevant for the measurement
of the spectrum. If such a measurement is made with short pulses, one obviously
integrates over all times (or sufficiently long times), thus an autocorrelation function
of the field is recorded. To obtain the spectrum one has to F OURIER transform this
signal which according to (I.17) leads to

1 (+ 2 ˜
F E − (t) E + (t) = E (ω) ∝ I (ω).
2π
I.4 Examples 649
If a prism spectrograph is used a similar argument can be based on the wave optical
interpretation of the index of refraction.
Hence, the definition of the spectrum according (I.26) is justified. Proper normal-
ization is provided by the P LANCHEREL theorem in the form (I.25), which simply
states energy conservation: the fluence F is independent of whether we integrate in-
tensity over all times or spectral intensity distribution over all angular frequencies.
The units are [F ] = J m−2 , [I (t)] = W m−2 , and [I˜(ω)] = J s m−2 , respectively.
It is important to note that the above use of P LANCHEREL’s theorem is only pos-
sible for square integrable functions, i.e. for pulses of electromagnetic radiation with
finite duration. If we want to describe CW light sources the integration over all times
has to be replaced by an average over a sufficiently long time Tav . P LANCHEREL’s
theorem (I.25) must then be replaced by
Tav /2 ∞
1 ε0 c Tav /2 + 2
I (t)dt = E (t) dt = I˘(ω)dω = I, (I.28)
Tav −Tav /2 2Tav −Tav /2 −∞
where I˘(ω) is now the spectral intensity of the ensemble, measured in units [I˘(ω)] =
W s m−2 , while I is the average intensity with [I ] = W m−2 . More about station-
ary, quasi-monochromatic or chaotic light sources, their spectra and their coherence
properties will be found in Sect. 2.1, Vol. 2.
I.4 Examples
In the following we shall present the most commonly used temporal and spectral
profiles of light pulses. The F OURIER transforms collected here can be derived
by analytic integration, where necessary with the help of a suitable computer pro-
gramme (e.g. SWP 5.5, 2005). They are also found in standard textbooks or at
the web (e.g. W EISSTEIN, 2012; W IKIPEDIA CONTRIBUTORS, 2014). We write the
field envelope as

E0 (t) = E0 h t/|t0 | with h(0) = 1 and (I.29)
ε0 c 2
I0 = E (I.30)
2 0
where E0 is the maximum field amplitude, |t0 | a characteristic width, and I0 the
cycle averaged maximum intensity.
We point out that the spectral intensity distribution as defined in (I.26) refers to a
single pulse. It has the dimension [I˜(ω)] = J s m−2 . Integrated over all frequencies
it gives the fluence F per pulse, i.e. the total pulse energy per unit area:
∞ ∞
F= I (t)dt = I0 h2 (t/t0 )dt. (I.31)
−∞ −∞
If one wants to extend the notion of the spectral intensity distribution to a CW

beam, one has to modify the normalization. As detailed in Sect. 2.1, Vol. 2, one
may assume that the beam consists of a statistical ensemble of single pulses which
are characterized by individual time constants τi and their individual spectra I˜i (ω).
One then has to average these spectra and to renormalize in respect of the average
duration τc of the pulses. One obtains an overall spectrum:

1 ∞
I˘(ω) = I˜i (ω) = w(τi )I˜i (ω)dτi . (I.32)
τc 0
This spectrum has now the dimension W s m−2 and the integration over all frequen-
cies gives the average, stationary intensity I of the beam.
I.4.1 Gaussian Distribution
Gaussian pulse shapes are probably the most popular ones, mainly due to their con-
venient mathematics. Starting from (I.18) we write the field envelope
2
t
E0 (t) = E0 h(t) = E0 exp − 2 (I.33)
τG
√
with a FWHM= 2 ln 2τG = 1.665τG . The corresponding cycle averaged intensity
(I.19) is now

t2
I (t) = I0 exp −2 2
τG
√
with a FWHM t1/2 = 2 ln 2τG = 1.177τG . (I.34)
We also note the overall fluence

∞
t2 π τG π
F = I0 exp −2 2 dt = ε0 cE0 =
2
τG I0 . (I.35)
−∞ τG 2 2 2
The F OURIER transform of the field envelope is again a Gaussian:

√ 1 2 2
(
E(ω) = τG π exp − τG ω and (I.36)
4

√
E ( − ωc )e−iφ = τG π exp − 1 τG2 (ω − ωc )2 − iφ .
(+ (ω) = E(ω (I.37)
4
Thus, with (I.26) the (experimentally measurable) intensity spectrum becomes
2
τG2 τ I0 ω − ωc 2
I˜(ω) = I0 exp − G (ω − ωc )2 = 2 exp − , (I.38)
2 2 ωG ωG
√
with ωG = 2/τG and a FWHM
√ √
ω1/2 = 2 ln 2ωG = 2 2 ln 2/τG = 2.355/τG . (I.39)
I.4 Examples 651
&∞
One easily verifies that −∞ I˜(ω)dω = F as in (I.35). In frequency space ν1/2 =
√
2 ln 2/(πτG ) and the so called time-bandwidth product is
2 ln 2
t1/2 ν1/2 = = 0.441. (I.40)
π
I.4.2 Hyperbolic Secant
Another, quite popular distribution function for describing the time dependence of
short light pulses is the hyperbolic secant
t E0 2E0
E0 (t) = E0 sech = = (I.41)
τs cosh(t/τs ) et/τs + e−t/τs
√
with a FWHM of −2 ln(2 − 3)τs = 2.634τs . The corresponding intensity distribu-
tion is
2
2
I (t) = I0 sech (t/τs ) = I0 t/τ
2
, (I.42)
e s + e−t/τs
√
with a FWHM t1/2 = −2 ln(−1 + 2)τs = 1.763τs . (I.43)
This normalization leads to a fluence

∞
F = I0 sech2 (t/τs )dt = 2τs I0 . (I.44)
−∞
The F OURIER transform of the field envelope is again a hyperbolic secant
( πτs ω 2E0 πτs

E(ω) = E0 πτs sech = πτ ω/2 or (I.45)
2 e s + e−πτs ω/2
(+ (ω) = E0 πτs e−iφc sech πτs (ω − ωc ) .
E (I.46)
2
The spectral intensity profile for a pulse with the carrier frequency ωc is

˜ ε0 c 2 πτs
I (ω) = 2 2
πE0 τs sech (ω − ωc ) . (I.47)
4 2
In angular frequency space it has a FWHM
√
ω1/2 = 4 arcsech(1/ 2)/(πτs ) = 1.122/τs (I.48)
and thus ν1/2 = 0.179/τs , so that the time-bandwidth product is
t1/2 ν1/2 = 0.315. (I.49)

I.4.3 Rectangular Wave-Train
For a number of situations a rectangular wave-train is a useful model of a light

pulse. Assume an (angular) carrier frequency ωc = 2π/Tc , let the pulse begin at
time t = ti and end at ti + τi ; during this time interval the amplitude is constant and
zero elsewhere, its relative phase φi may be chosen freely. In our standard format
(I.18) the electric field of the wave is explicitly

1 E0 ei[ωc (t−ti )−φi ] for ti < t < ti + τi
E i (t) = e∗ + c.c. (I.50)
2 0 else
The intensity distribution has the same temporal shape with I0 = ε0 cE02 /2. It is
convenient to directly evaluate the F OURIER transform (I.24) of Ei+ (t):
t0 +τr

(+ (ω) = E0
E exp i(ωc t − ωc ti − φi − ωt) dt
i
t0

exp[i(ωc − ω)τi ] − 1
= E0 τr exp −i(ωti + φi ) (I.51)
i(ωc − ω)τi
(i (ω) = E0 τi exp[−iωti ] 1 − exp[−iωτi ] .

E (I.52)
iωτi
The spectral intensity distribution (I.26) is thus

ε0 c (+ 2 I0 τi2 τi (ω − ωc )
I˜i (ω) = Ei (ω) = sinc2 , (I.53)
4π 2π 2
with the sinc x = (sin x)/x function. The overall fluence is
∞ ∞
F= I (t)dt = I˜(ω)dω = I0 τi .
−∞ −∞
The FWHM of I˜i (ω) is given by ω1/2 = 5.566/τi or in frequency space ν1/2 =
0.886/τi so that the time-bandwidth product is
t1/2 ν1/2 = 0.886, (I.54)
which is much broader than for the Gaussian or sech2 distributions.

Finally, we note in passing that all above expressions apply to a simple rectangu-
lar pulse (without oscillations) when one just sets ωc = 0 and φi = 0.
I.4.4 Rectangular Spectrum
Another important case is a rectangular spectrum. Such a situation may arise, e.g.
if one spectrally filters a broad band light CW source with a sharp band-pass filter
(e.g. in stellar interferometry). The spectrum would then be
I.4 Examples 653

I /ω for ωc − 12 ω < ω < ωc + 12 ω
I˘(ω) = (I.55)
0 else,
where I is the average stationary intensity of the beam. The integral (I.3) can easily
be carried out in this case and one obtains the inverse F OURIER transform:

I iωc t ωt sin x
F −1 I˘(ω) = e sinc with sinc(x) = . (I.56)
2π 2 x
This formula turns out to be useful e.g. for understanding stellar interference spec-
troscopy (see Sect. 2.1.4, Vol. 2).
I.4.5 Exponential and LORENTZ Distributions
The One-Sided Exponential Distribution

0 if x < 0
h(x) = (I.57)
exp(−x) if x ≥ 0
is used to describes an exponentially decaying field (oscillating at a carrier fre-
quency ωc ) and its cycle averaged intensity, respectively:

t
E(t) = E0 h and
2τe

t
I (t) = I0 h with FWHM t1/2 = τe ln 2 = 0.693τe . (I.58)
τe
The overall fluence is simply F = τe × I0 .

The F OURIER transform of the field envelope is complex in this case (asymmetric
distribution):
( 2τe E0
E(ω) = , and
1 + 2iτe ω
(+ (ω) = e−iφ 2τe E0

E .
1 + 2iτe (ω − ωc )
The intensity spectrum becomes a L ORENTZ distribution
1 I0 τe2 I0 γ 2 /4
I˜(ω) = = , (I.59)
π 1 + [2τe (ω − ωc )]2 πγ 2 γ 2 /4 + (ω − ωc )2
with a FWHM ω1/2 = γ = 1/τe . (I.60)
In frequency space this gives ν1/2 = 1/(2τe π) = 0.159/τe , so that the time-
bandwidth product becomes
t1/2 ν1/2 = 0.110. (I.61)
This is an extraordinarily small time-bandwidth product in comparison with the

Gaussian or sech2 case. Note, however, that the temporal shape of this “pulse”
is
& characterized by an extremely wide & ∞ wing at positive times. Normalization
I˜(ω)dω = F is verified easily with −∞ dx/(1 + x 2 ) = π .
The Two Sided Exponential Distribution

E0 (t) = E0 exp −|t|/(2τee ) (I.62)

is a somewhat pathological pulse envelope, with

E + (t) = E0 exp i(ωc t − φ) − |t|/(2τee ) . (I.63)
It has an intensity profile

I (t) = I0 exp −|t|/τee (I.64)
with a fluence F = 2I0 τee , (I.65)
and a FWHM t1/2 = 2 ln 2τee = 1.386τee .

Die F OURIER transform of the field envelope is now a (real) L ORENTZ distribu-
tion
( 4τee E0
E(ω) = , or alternatively (I.66)
1 + (2τee ω)2
(+ (ω) = E0 e−iφ γ
E , (I.67)
γ 2 /4 + (ω − ωc )2
with an FWHM γ = 1/τee . The intensity spectrum is given by
2
˜ I0 γ
I (ω) = (I.68)
2π γ 2 /4 + (ω − ωc )2

√
with a FWHMω1/2 = 2 − 1γ = 0.644γ = 0.643/τee , (I.69)
so that the time-bandwidth product becomes in this case

√
tL ν1/2 = 2 − 1(ln 2)/π = 0.142. (I.70)
We point out that (I.68) is not a L ORENTZ profile, and may, e.g. not easily be convo-
luted. We emphasize that in any case this is not a typical profile for characterizing a
real light pulse: it has a cusp at time zero and extremely wide tails, both in the time
and in the frequency domain.
I.5 Fourier Transform in Three Dimensions 655
For reference we also write (I.67) in normalized form

1 γ
L̃(ω, γ ) = (I.71)
2π γ /4 + (ω − ωc )2
2
&∞
with −∞ L̃(ω, γ )dω = 1. The inverse FT is given by (I.63) as
∞

1 1 −γ |t|/2+iωc t
F −1 L̃(ω, γ ) = L̃(ω, γ )eiωt dω = e (I.72)
2π −∞ 2π
with γ = 1/τee . We have set here φ = 0.
We finally can now supplement the proof for the additivity of linewidths when
convoluting two L ORENTZ profiles, as introduced by (G.21). According to (I.12) the
inverse FT of a convolution of two L ORENTZ profiles is proportional to the products
of their inverse FT:

F −1 L̃1 (ω, γ1 ) ∗ L̃1 (ω, γ2 ) (I.73)

1 −γ1 |t|/2−iω1 t 1 −γ1 |t|/2+iω2 t 1 −(γ1 +γ2 )|t|/2+i(ω2 −ω1 )t
= 2π × e × e = e .
2π 2π 2π
Now we just transform this back, compare with (I.72), and obtain:
1 −(γ1 +γ2 )|t|/2+i(ω2 −ω1 )t
L1 (x, γ1 ) ∗ L1 (x, γ2 ) = F e (I.74)

2π
2 (γ1 + γ2 )2 /4
= .
(γ1 + γ2 )π (x − (ω2 − ω1 ))2 + (γ1 + γ2 )2 /4
Thus, the convolution of one L ORENTZ profile with another one leads again to a
L ORENTZ profile. The FWHM of the two profiles are just added:
γ = γ1 + γ2 . (I.75)
I.5 Fourier Transform in Three Dimensions
F OURIER transforms can be extended into n dimensions. Three dimensional FTs

will be employed when 3D wave-packets are introduced (Eq. (1.106) in Sect. 1.4,
Vol. 2). There, in principle, one has to integrate over plane waves exp(−ikr) in full
momentum space k. The same holds for FBA (see Sects. 6.6, 8.2, and 8.4.4, Vol. 2).
Practical evaluation of these 3D FTs and their inverse is significantly more complex
than in one dimension. Complete operational tool-sets for the 2D and 3D cases have
recently been developed by BADDOUR (2009) and (2010), respectively. We briefly
summarize some key results for the 3D case.
The definition of the 3D F OURIER transform – in analogy to (I.2) – reads

( (
X(k) = X(kx , ky , kz ) = X(r)e−ikr d3 r (I.76)
R3
and its inverse – in analogy to (I.3) – is

1 (
X(r) = X(x, y, z) = X(k)e ikr 3
d k. (I.77)
(2π)3 R3
We note in passing that the D IRAC delta function in three dimensions is

1
δ k−k = ei(k−k )r d3 r. (I.78)
(2π)3 R3
Its characteristic property is expressed by

f (x) = f x δ x − x d3 x
R3
∞
2π π
= dϕ sin θ dθ f x δ x − x x 2 dx , (I.79)
0 0 0

specifically this ensures δ x − x d3 x = 1. (I.80)
R3
In view of (I.79) one may also express the 3D delta function as
δ(x − x )
δ x − x = 2 δ θ − θ δ ϕ − ϕ . (I.81)
x sin θ
For problems with some kind of spherical symmetry (e.g. in atomic physics)
it is useful to rewrite (I.76) in spherical polar coordinates, with standard position
coordinates (r, θr , ϕr ) and coordinates in wave vector space (k, θk , ϕk ):
2π π ∞
( θk , ϕk ) =
X(k, X(r, θr , ϕr )e−ikr r 2 sin θr drdθr dϕr . (I.82)
0 0 0
One expands X(r, θr , ϕr ) into a series of spherical harmonics
∞

X(r) = X(r, θr , ϕr ) = Xm (r)Ym (θr , ϕr ), where (I.83)
=0 m=−
2π π
∗
Xm (r) = X(r, θr , ϕr )Ym (θr , ϕr ) sin θr dθr dϕr . (I.84)
0 0
By expanding also the plane wave (I.82) according to (J.13) one obtains the 3D
F OURIER transform in k space
∞

( = X(k,
X(k) ( θk , ϕk ) = 4π (−i) X m (k)Ym (θk , ϕk ), (I.85)
=0 m=−
with the th order spherical H ANKEL transform of Xm (r)

∞

Xm (k) = S Xm (r) = Xm (r)j (kr)r 2 dr. (I.86)
0
The inverse 3D F OURIER transform – in analogy to (I.3) – is defined as

∞
1 (
X(r) = X(k)eikr 3
d k, (I.87)
(2π)3 −∞
which – complementary to (I.82) – may again be expressed in spherical coordinates.
(
Explicitly, one expands X(k) into a series of spherical harmonics
∞

( = X(k, θk , ϕk ) =
X(k) (m (k)Ym (θk , ϕk ),
X where (I.88)
=0 m=−
2π π
(m (k) =
X ( θk , ϕk )Ym
X(k, ∗
(θk , ϕk ) sin θk dθk dϕk . (I.89)
0 0
Using now the inverse spherical H ANKEL transform of X(m (k)

( 2 ∞(
X m (r) = X(k)j (kr)k 2 dk, (I.90)
π 0
one finally obtains the inverse 3D F OURIER transform in spherical coordinates:
∞
1 (

X(r) = X(r, θr , ϕr ) = (i) X m (k)Ym (θk , ϕk ). (I.91)
4π
=0 m=−
Comparing (I.85) and (I.88) one also finds that

(m (k) = 4π(−i) Xm (k) = 4π(−i) S Xm (r)
X
from which the F OURIER expansion coefficients may be obtained.

CW: ‘Continuous wave’, (as opposed to pulsed) light beam, laser radiation etc.
FBA: ‘First order B ORN approximation’, approximation describing continuum
wave functions by plane waves; used in collision theory and photoionization (see
Sect. 6.6 in Vol. 2 and Sect. 5.5.2, respectively).
FT: ‘F OURIER transform’, see Appendix I.
FWHM: ‘Full width at half maximum’.
SVE: ‘Slowly varying envelope’, approximation for electromagnetic waves (see
Sect. 1.2.1, specifically Eq. (1.38), Vol. 2).
References
BADDOUR, N.: 2009. ‘Operational and convolution properties of two-dimensional Fourier trans-
forms in polar coordinates’. J. Opt. Soc. Am. A, 26, 1767–1777.
BADDOUR, N.: 2010. ‘Operational and convolution properties of three-dimensional Fourier trans-
forms in spherical polar coordinates’. J. Opt. Soc. Am. A, 27, 2144–2155.
SWP 5.5: 2005. ‘Scientific work place’, Poulsbo, WA 98370-7370, USA: MacKichan Software,
Inc. http://www.mackichan.com/, accessed: 9 Jan 2014.
W EISSTEIN, E. W.: 2012. ‘Fourier transform’, Wolfram Research, Inc., Champaign, IL, USA.
http://mathworld.wolfram.com/FourierTransform.html, accessed: 9 Jan 2014.
W IKIPEDIA CONTRIBUTORS: 2014. ‘Fourier transform’, Wikipedia, The Free Encyclopedia.
http://en.wikipedia.org/wiki/Fourier_transform, accessed: 9 Jan 2014.
Continuum
J
J.1 Normalization of Continuum Wave Functions
Many physical problems require the inclusion of continuum states in addition to

discrete bound states – e.g. scattering processes, photoionization, electron impact
ionization an the like. In all these cases the normalization of the continuum states
poses a specific problem. We briefly indicate here how this problem may be solved
– as one way among several possible approaches.
For the discrete spectrum the radial wave functions Rn (r) are normalized in the
usual fashion:

Rn (r)Rn (r)r 2 dr = un (r)un (r)dr = δnn . (J.1)
In the following we use the radial functions in the form u(r) = rR(r). In the con-
tinuous spectrum, following B ETHE and S ALPETER (1957) Eq. (4.11ff), they are
normalized in T scale by demanding
∞ T +T
druT (r) uT (r)dT = 1. (J.2)
0 T −T
Here T (k) is any function of the electron wavenumber k in the continuum, possibly
k itself. In the theoretical treatment of photoionization normalization in scale is
frequently used, with being the energy of the electron in the continuum. The in-
tegration over dT needs only to be over a small interval 2T around T , since all
other contributions cancel.1
With such normalized continuum functions one may represent any wave function
including the continuum as partial wave expansion (for simplicity written here only
for one electron systems):
1 Summation of (J.1) over all n states in the discrete spectrum would be the equivalent to this second
integration in (J.2). Since only one state contributes, the result is also =1.

660 J Continuum
ϕ(r, θ, ϕ) (J.3)
) ∞ *
1 ∞
= Ym (θ, ϕ) anm un (r) + dT (k)am (T )uT (r) .
r k=0
m n=+1
The relation between normalization in T scale and in k scale is given by

−1/2 1/2
dT dk
uT (r) = uk (r) × = uk (r) × . (J.4)
dk dT
Specifically, for normalization in energy scale, with

2 k 2 me a02 k 2 M̄ 1 2
= = Eh and k = (J.5)
2M̄ M̄ 2 me a0 Eh
(for a system with reduced mass M̄) we obtain

d me dk M̄ 1 M̄ 1
= Eh a02 k and = = . (J.6)
dk M̄ d me Eh a02 k me a0 (2Eh )1/2
And for electrons with M̄ me and = k 2 /2 we obtain most simply in a.u.
d/dk = k. (J.7)
To illustrate this by way of example, we discuss a general radial wave function in

the continuum. In a.u. it is asymptotically (see e.g. B URKE, 2006)

Z
u (r) = b sin kr − π/2 + ln(2kr) + σ + δ . (J.8)
k
Here Ze is the charge of a C OULOMB field (if present) which enters into σ =
arg Γ ( + 1 − iZ/k) and the slowly varying logarithmic C OULOMB phase. The
standard phase shift δ reflects the influence of further, non-Coulombic interactions.
For a free particle (Z/k) ln(2kr) as well as σ and δ vanish. To obtain the normal-
ization factor b in k scale normalization, we neglect the logarithmic phase, write
δ̃ = −π/2 + σ + δ , and evaluate
k+k k+k
b
dk u (r) = i dk exp i k r + δ̃ − c.c.
k−k 2 k−k
sin kr
= 2b sin(kr + δ̃ ) .
r
Inserting this into (J.2), and substituting the rapidly oscillating term sin2 (kr + δ̃ )
by its average value 1/2, one may integrate over all r
∞
sin kr π
2b 2
dr sin(kr + δ̃ ) sin(kr + δ̃ ) = b2 ,
0 r 2
J.2 Plane Waves in 3D 661
&∞ √
where the identity 0 sin(|a|r)
r dr = π2 has been applied, so that b = 2/π . Hence,
normalized in k scale the radial wave function becomes

2 Z
u (r) = sin kr − π/2 + ln(2kr) + σ + δ . (J.9)
π k
To determine the dimension of uk (r), we write the units in the expression under
the integral in (J.2) [udrdk] = 1, or as dimensional equation u2 L1 L−1 = 1 so that
u = 1, i.e. uk (r) in k scale normalization is dimensionless. For clarity it might be
useful to explicitly write out the a.u., i.e. to replace r → r/a0 and Z/k → Z/(ka0 )
in (J.9), so that the expression becomes independent of the units used.
For normalization in scale we use (J.4)–(J.7) and obtain in a.u.:

2 dk Z
u (r) = sin kr − π/2 + ln(2kr) + σ + δ
π d k

2 Z
= sin kr − π/2 + ln(2kr) + σ + δ or explicitly (J.10)
πk k

2 me Eh /2 1/4 Z
= sin kr − π/2 + ln(2kr) + σ + δ .
πEh a0 M̄ ka0
(J.11)
The latter expression is independent of the units used. The prefactor (Eh a0 )−1/2
is again obtained from a dimensional analysis: normalized in scale from (J.2)
we have [u2 drd] = 1, so that u2 = Enrg−1 L−1 and u = Enrg−1/2 L−1/2 . Note that
for electron scattering the mass factor me /M̄ 1 disappears. Different authors use
slightly different notations and energy units (often without mentioning which).2
J.2 Plane Waves in 3D
J.2.1 Expansion in Spherical Harmonics
Without proof we note that a plane wave in 3D can be written as
∞

∗
ψ (k) (r) = eik·r = 4π i j (kr) Ym (θk , ϕk )Ym (θr , ϕr ), (J.13)
=0 m=−
2 For example, expression (J.11) was introduced by C OOPER (1962) to photoionization as

uε (r) → π −1/2 ε −1/4 sin ε 1/2 r − π/2 + Zε 1/2 ln 2ε 1/2 r + δ . (J.12)
Here, ε = 2/Eh , i.e. energies are measured in RYDBERG units = Eh /2, lengths in a0 .
662 J Continuum
with the polar coordinates (r, θr , ϕr ) representing r, while (k, θk , ϕk ) gives the mag-
nitude and direction of the wave vector k, and j (kr) = u (kr)/(kr) are spherical
B ESSEL functions. They are solutions of the radial S CHRÖDINGER equation (2.110)
for vanishing potential:
2
1 d2 u k ( + 1)
− + u (r) = 0. (J.14)
2 dr 2 2 2r 2
As one easily verifies, the most simple ones are:
sin x sin x cos x
j0 (x) = sinc x = and j1 (x) = − . (J.15)
x x2 x
All others may in principle be derived from the recursion formula:
2 + 1
j+1 (x) = j (x) − j−1 (x). (J.16)
x
Asymptotically the following relations hold:

x /[(2 + 1)(2 − 1)(2 − 3) · · · ] for x
j (x) = . (J.17)
sin(x − π/2)/x for x
With the addition theorem (C.22) and the angle γ between k and r one may also
write (J.13) as:
∞

ψ (k) (r) = eik·r = (2 + 1)i j (kr)P (cos γ ). (J.18)
=0
J.2.2 Normalization in Momentum and Energy Scale
The probability density |ψ (k) |2 of the plane waves (J.13) or (J.18) is given per
wavenumber to the third power (dimension L3 ) and per volume (L−3 ), so they are
overall dimensionless. They may be normalized in k scale (see e.g. OVCHINNIKOV
et al., 2004):
1
((k) (r) =
ψ eik·r =
r|k. (J.19)
(2π)3/2
To verify this normalization we first integrate over position space using (I.78):

k 2 |k 1 k = ψ((k)∗ (r)ψ
((k) (r)d3 r a03 δ ka0 − k a0 .
2 1
This is the continuum equivalent to the usual orthogonality

a|b = δab of bound
state wave functions. Since ka0 is dimensionless, the expression is given per
wavenumber interval cubed (dimension L3 ) and thus reflects the built in density
of states. Finally, with (I.80), integration over k spaces confirms the correct normal-
ization of (J.19):

3
k k k d k = a03 δ ka0 − k a0 d3 k ≡ 1.
To obtain 3D normalization in the scale, we note that

dk
d3 k = k 2 dkdΩ = k 2 ddΩ.
d
Hence (J.4) becomes in 3D
1/2
dk
((k) (r) = k
ψ ((k) (r).
ψ (J.20)
d
Specifically for conversion into energy scale with (J.6)

1
d3 k = kddΩ, (J.21)
Eh a02
holds, and the 3D plane wave (J.19) normalized in energy scale becomes

ka0 ik·r
ψ( (r) = (2π)
(k) −3/2
e . (J.22)
a03 Eh
((k) (r)|2 is
Its dimension is now Enrg−1/2 L−3/2 so that the probability density |ψ
correctly given per energy and volume.

References
B ETHE, H. A. and E. E. S ALPETER: 1957. Quantum Mechanis of One- and Two-Electron Atoms.
Berlin, Göttingen, Heidelberg: Springer Verlag, 369 pages.
B URKE, P.: 2006. ‘Electron-atom, electron-ion and electron-molecule collisions’. In: G. W. F.
D RAKE, ed., ‘Handbook of Atomic, Molecular and Optical Physics’, 705–729. Heidelberg, New
York: Springer.
C OOPER, J. W.: 1962. ‘Photoionization from outer atomic subshells. A model study’. Phys. Rev.,
128, 681–693.
OVCHINNIKOV, S. Y., G. N. O GURTSOV, J. H. M ACEK and Y. S. G ORDEEV: 2004. ‘Dynamics of
ionization in atomic collisions’. Phys. Rep., 389, 119–159.
Index of Volume 1
Symbols Adjoint operator, 97, 576

1, identity matrix, 99 ADK theory, 437
3D F OURIER transform, 655–657 Air mass coefficient (AM), 36
3j symbols, 300, 564–568 A IRY function, 280
orthogonality, 565, 566 Al atom, G ROTRIAN diagram, 518
special cases, 567, 568 Alignment, 173, 588, 620
symmetries, 565, 566 angle, 173
6j symbols, 311, 568–572 parameter, 620
orthogonality, 569, 570 Alkali atoms, 144, 146, 151, 165
special cases, 571, 572 comparison with H atom, 146
symmetries, 569, 570 overview about term energies, 146
9j symbols, 572 quantum defect, 146, 147
spectroscopy, 145, 146
A Alkaline earth metals
Above-barrier ionization, 436, 437 fine structure, 361, 362
Above-threshold ionization (ATI), 266, 441 G ROTRIAN diagram, 371
of Ar, 441 Angular dispersion, 275
of C60 , 441, 442 Angular momentum, 5, 65, 66, 72, 107–117
Absorption, 193–196 algebra, 575–592
coefficient, 18, 241, 422 commutation rules, 559
molar, 18 conservation, 81
cross section, 18, 240–242 E1-transitions, 196
broad band light, 242 coupling, 297, 298
monochromatic light, 241 definition, 109, 559–573
definitions, units, 180 eigenstates, 561
edge, 521, 525 intrinsic, 78
E INSTEIN coefficient, 180 matrix elements, 561
inner shells, 520–524 operators, 109, 111
introduction, 17, 18, 178–180 scalar product, 298, 299, 585, 586
probability, 190–192 projection theorem, 578
rate, 179, 191 real and helicity basis, 560
X-ray, 520–525, 530 Anomalous magnetic moment of the electron,
C OMPTON scattering, 526 331
pair production, 526 Anomalous Z EEMAN effect, 380
photoionization, 526 Anti-symmetrization, 346, 357, 358, 388
T HOMSON scattering, 526 Areas of physics, 2
Addition theorem for Ckq , 579 Atom model, 63

666 Index of Volume 1
Atom radius, 121 B OSE -E INSTEIN condensate, 8

Atomic beam, 73–75, 282, 317 B OSE -E INSTEIN statistics, 23
Atomic core, 148 Boson, 20, 22, 139
Atomic form factor, 41, 430, 431 Boundary condition, 104
Atomic hydrogen B RAGG reflection, 40, 41
eigenfunctions, 123–126 B REIT-R ABI formula, 393, 468
Atomic orbitals, 118, 122, 125, 126 Z EEMAN effect in hyperfine structure,
Atomic radius, 29, 68, 143, 144 467–471
Atomic size, 64 Bremsstrahlung (X-ray), 530
Atomic units, 67, 68, 118, 119 B RILLOUIN zone, 41, 133
Atoms in a magnetic field, see Z EEMAN effect
Atoms in an electric field, see S TARK effect C
Atoms in intense laser fields, 432, 442 C atom, 22
Attometer, 6 G ROTRIAN diagram, 514
Attosecond, 8 Candela, 38
Attosecond laser pulses, 440 CCD camera, 59, 269, 277
Aufbau principle, 138, 139 Central field approximation, 496
AUGER electron, 522 Centre of mass system, 119
Autocorrelation function, 623, 626, 628, 646, Centrifugal potential, 117, 120, 123
648 Centrosymmetric problems, 108
Autoionization, 260, 366–370 Cesium fountain atomic clock, 320
Avoided crossing, 392–394 Characteristic X-ray radiation, 530
S TARK effect in RYDBERG states, 411 Chemical shift
B NMR spectroscopy, 488
Band structure, 28 Chemical-potential, 23, 24, 105–107
electronic, in a solid, 132 Classical forced oscillator
Barions, 48, 49 model for photon absorption cross section,
Barn, 524 240
Basis spin function, 115 C LAUSIUS -M OSSOTI formula, 421
Basis states: real and complex, 595–599 C LEBSCH -G ORDAN coefficients, 300,
Basis vectors, 95 564–568
G ROTRIAN diagram, 372 orthogonality, 565, 566
BESSY, 42, 532 symmetries, 565, 566
β (anisotropy) parameter, 260, 263, 264, 269, CODATA, 9, 321, 329, 330, 334–336, see also
529 Fundamental physical constants
B EUTLER -FANO profile, 368 data bank, 551
Black body radiation, 31–34 Coherently excited states, 217–220
Blazed grating, blaze angle, 277 Collisional line broadening, 233, 234
B LOCH wave function, 132 Colour temperature, 39
B OHR, 2, 64 Commutation rules, 114, 115, 634
magneton, 378, 449 Commutator, 96, 101
model of the atom, 64–70 Complex spectra, 512–519
comparison with quantum mechanics, C OMPTON effect, 2, 28, 29
127, 128 C OMPTON wavelength, 29
limits, 69, 70 Configuration interaction (CI), 363–366, 508,
orbital radius, 67, 124 509
B OLTZMANN Continuum, 659–663
constant, 19, 33 normalization, 659–661
distribution, 20, 24, 25, 235, 624, 627 of eigenvalues, 102
factor, 23 wave function, 262
statistics, 21–23 Convolution, 623–629
B ORN approximation Gaussian profile, 626, 627
first, applied to photoionization, 257 Hyperbolic secant, 627, 628
first, for X-ray photoionization, 524 L ORENTZ profile, 628, 654
Index of Volume 1 667
theorem for F OURIER transform, 645 Density of states, 21–24, 238, 240
VOIGT profile, 628, 629 particle in a box, 105, 106
C OOPER minimum, 260, 529 Detailed balance
Coordinate rotation, 575, 605–611 principle of, 184
exercise, 207 Detuning, 229
Coordinate system Diamagnetism, 396–398
atomic vs. photon, 174 Dielectric function, 57
cartesic and polar, 108 Diffraction
electron vs. nucleus, 295 D EBYE-S CHERRER, 58, 59
Core electron, 148, 151 experiment, 60
Core potential, 149 He scattering, 60
alkali atoms, 165 image, 42
Correlation function LEED, 59
1st order, 625 Dimensional analysis, 119, 192, 554, 556, 661
Correspondence principle, 127 Dipol vector, 183
C OULOMB gauge, 631 Dipole approximation, 189, 631–640
C OULOMB integral, 356, 359, 365, 506 electric, 635
C OULOMB law, 50, 59 magnetic, 250–254
C OULOMB potential, 119, 121, 123 Dipole excitation, linear combination of states,
H atom, 121 217–225
screened, 148, 149 Dipole matrix element, 193
C OULOMB wave, 262 length approximation, 193, 636
Coupling
velocity approximation, 193, 636
jj , 301, 354, 360
Dipole operator, 594
LS, 301, 307, 354, 360, 361
magnetic field, 386
LS vs. jj , 512–514
multi-electron system, 264, 363
RUSSEL -S AUNDERS, 301, 354, 360, 361,
Dipole oscillator, classical, 182
508
Dipole radiation
break down, 362
angular characteristic, 203–212
spin-orbit, see Spin-orbit
Crystal lattice, 40 Dipole transition
C URIE constant, 396 amplitude, 193
C URIE’s law, 396 E1 transitions in the H atom, 201–203
Cyclotron frequency, 54, 332 in He, 362–365
electron, 79 length approximation, 636
Cylindrical capacitor, 52 matrix element, 190, 635
operator, 190, 193, 263
D selection rules for E1 transitions,
Damping constant, 229 196–203
DARWIN term, 305 selection rules for E1-transition, 202
D E B ROGLIE, 57, 89 velocity approximation, 636
wavelength, 57–59 D IRAC delta function, 644
Decay constant, 15 D IRAC equation, 79, 93, 296, 303, 333
Decay rate, 15 Direct product, 578
Degeneracy, 21, 22 Dispersion, 421
, 123 anomalous, 422
m, 111 close to resonance, 232, 233
, removal of, 137–146 normal, 420, 422
m, removal of, 130, 131 Dispersion relation, 131–134
Degree of coherence matter waves, 94
1st order, 625 Displaced terms
Degrees of freedom, 19 alkaline earth term schemes, 372
Density distribution, 125 C atom, 515
Density functional theory, 510–512 Ne atom, 518
D OPPLER free spectroscopy, see Spectroscopy, Electron, 49–51, 114

D OPPLER free angular momentum, 50
D OPPLER broadening, 234, 236, 285 classical electron radius, 50
D OPPLER effect, 285, 317 C OMPTON wavelength, 29
classical, 14 elementary charge, 50, 51
quadratic, 13 g factor, 79
relativistic, 13 mass, 68
D OPPLER narrowing, 283 M ILLIKAN experiment, 50
D OPPLER profile, 287 orbital magnetic moment, 129
Double slit experiment, YOUNG’s, 88, 89 point like, 49
Doubly excited states, 348, 365–367 spin, 50, 70, 78, 112, 114, 128
Drehimpuls, 81 Electron bunches, 532
Dressed states, 418 Electron configuration, 138, 142, 144, 151,
D RUDE frequency, 57 302, 500, 508, 509
Duality Electron diffraction
wave-particle, 2, 4 D EBYE-S CHERRER, 58, 59
Duality, wave-particle, 58 LEED, 59
Electron hole, 521
E Electron magnetic moment, 50, 79, 81, 294,
E1-transitions, 635 387, 449
Echelle spectrometer, 277 anomaly, 331, 336
Effective mass of an electron, 132 Electron shell, 139, 140
Effective nuclear charge, 159 Electron spin, 114–116
Effective potential, 117 resonance spectroscopy (ESR), see
Eigenenergy, 91 Electron paramagnetic resonance
Eigenfunction, 91, 99 (EPR)
nodes of the, 103 Electron storage ring, 53
of momentum, 102 synchrotron radiation, 531
Eigenstate, 98, 99 Electronvolt, 51
Eigenstates of angular momentum, 109–113 Electrostatic potential, expansion, 614–616
Eigenvalue, 97 Electroweak interaction, 44
Eigenvalue equation, 97, 99 Ellipticity angle, 172, 174
energy, 129 Emission, 193–196
z , 110
of L inner shells, 520–524
of momentum, 102 spectrum, 130
Eigenvalue problem, 102 Emittance, 532
Eigenvector, 97, 99 Energy analyzer, 52, see also Energy selector
E INSTEIN Energy balance, 120
E = mc2 , 3, 10 Energy conservation
photoelectric effect, 31 operator form, 91
E INSTEIN A and B coefficients, 184, 185, 193, relativistic, 11, 28
194, 212, 215, 216, 228, 230, 241, Energy levels
314, 489 fine structure splitting, 294
E INSTEIN’s paradigm on speed of light, 425 Energy packet, 27
E INSTEIN - DE -H AAS effect, 79, 81 Energy quantization, 26
Electric dipole (E1) transitions, 588 Energy scales, 7
Electric dipole moment Energy terms
of the electron-nucleus pair, 189 H atom, 122
Electric quadrupole (E2) transition, 250–254, Energy zero
588 H atom, 118
Electric quadrupole moment Entanglement, 354, 609, 610
atomic nuclei, 449 EPR spectroscopy, 484–487
Electromagnetic spectrum, 31 high B field, 487
Electromagnetic waves, 170–176 X band, 486
Equivalence of mass and energy, 10 relativistic correction, 304, 305

Ergodicity, 626 spin-orbit term, 306
Error function H atom, 293, 296, 297, 306, 307
complementary, 629 He and He like ions, 360, 361, 362
complex, 629 interaction, see Spin-orbit interaction
E ULER angles, 605 interval rule (L ANDÉ), 308, 361, 362, 372
Exchange Hg atom, 372
boson, 44 Na D doublet, 293
integral, 356, 357, 359, 365 normal ordering of terms, 308
interaction, 343 quantum defect, 308, 309
spin orientation, 358, 360 splitting, 293, 308
operator, 351–353 theory and experiment, 303–310
Expectation value, 98, 99, 126 transitions
observable, 98 branching ratios, 315
r k for the H atom, 126, 127 multiplet, 312, 315
spin component, 115 transitions and selection rules, 310–316
the momentum in a 1D box, 103 Fine structure constant, 9, 69, 293, 296
Experiment of B ETH, 176 electromagnetic coupling, 326
Extinction coefficient, 241, 421 high precision measurement, 335
molar, 18 Finesse, see FABRY-P ÉROT interferometer
Four vector (momentum), 11
F F OURIER transform, 643–658
FABRY-P ÉROT interferometer, 279–281 analysis, 54
finesse, 280 exponential distribution, 653–655
finesse coefficient, 280 Gaussian, 650, 651
FADEEVA function, 629 inverse, 643
FANO lineshape(, 366 L ORENTZ, 653–655
FANO lineshape, 369 rectangle, 652
Fast light, 422–427 sech, 651, 652
F ERMI contact term, 456, 458, 459 spectroscopy, 643
F ERMI energy, 25, 106 Free electron gas, 105–107
F ERMI level, 107 Free electron laser (FEL), 542, 543
F ERMI’s golden rule, 238 Free spectral range, 279
F ERMI -D IRAC statistics, 23, 106 FT-ICR, 54, 55
Fermion, 20, 22, 44, 138 Fundamental interactions
Ferromagnetism, 80, 358 the four, 43–51
F EYNMAN diagrams, 324–326 Fundamental physical constants, 67, 551, 553
energy conservation, 326
for ge − 2, 335 G
L AMB shift, 326 g − 2, see Electron magnetic moment, anomaly
neutron decay, 49 Galaxy, 6
pair annihilation, 325 Gas kinetic cross section, 20
pair generation, 325 Gaussian profile, 235
propagator, 326 convolution, 626, 627
self-energy of the electron, 325 Generalized cross section for multi-photon
vacuum polarization, 325 processes, 245
vertices, 326 Geonium atom, 333–335
Fine structure, 293–316 gJ factor
alkali atoms, 307, 309 definition, 77
alkaline earth metals, 362, 372 quantum mechanical derivation, 380, 381
and electron spin, 293 vector model, 381, 382
BALMER Hα line, 288 Gratings, 274–279
D IRAC theory, 303 G ROTRIAN diagram, 514–518, 520
DARWIN term, 305 Al atom, 518
alkaline earth atoms, 371 ground state, 348

Be atom, 372 H AMILTON operator, 345
C atom, 514 He like ions
H atom, 202 ground state, 349
He atom, 343 H EISENBERG representation, 100
Hg atom, 372 H EISENBERG uncertainty relation, 100, 101
Li atom, 145 Helicity, 196
N atom, 515 Helicity basis, 171, 172, 174, 267, 560
Ne atom, 517 angular momentum, 560
O atom, 516 transition amplitudes, 198–200
Ground state Hemispherical capacitor, 52
H atom, 64 Hermitian operator and conjugate, 97, 576
Group in periodic system of elements, 140 HFS, see Hyperfine structure
Group index, 424 Hg atom, 372–374
Group velocity, 422–424 G ROTRIAN diagram, 372
Gyromagnetic ratio, 71 High harmonic generation, 439, 440
plateau, 440
H H ILBERT space, 100
H atom, 69, 117–128, 296, 302, 305, 306, History of physics, 2, 3
316 Hole burning, 284, 285
1S–2S transition, 290, 291 H UND’s rules, 357
BALMER series, 126 H UYGENS -F RESNEL principle, 89
density plots, 124–126 Hydrogen anion, 350
energy levels, 122 Hydrogen like ions, 68
expectation values of r k , 126, 127 Hydrogen maser, 459
fine structure, 287 H YLLERAAS wave function, 350
fine structure transition, 310 Hyperbolic secant
H AMILTON operator, 117 convolution, 627, 628
in a magnetic field, 129 Hyperfine structure, 287, 447–493
L AMB shift, 317 coupling constant, 452
LYMAN series, 126 coupling tensor, 456, 457, 480
orbitals, 125 deuterium, 454, 460
PASCHEN series, 126 E1 multiplet transitions, 460
radial wave function, 120, 121, 123, 124 H atom, 453, 459
spectrum, 65, 69, 126 intervall rule, 481
wave functions (2D plot), 125 isotope shift and electrostatic interaction,
Hadrons, 49 471–482
H AMILTON operator, 91–94, 99, 101, 117, L ANDÉ’s interval rule, 452
121, 130 magnetic dipole and quadrupole, 481
He atom, 345 magnetic dipole interaction, 452
magnetic fields, 129 mass effect, 473, 474
H ANKEL transform Na atom, 282, 287, 290, 454, 460
spherical, 657 nuclear quadrupole moment, 477–481
H ARTREE equations, 498–500 quadupole interaction, 481
H ARTREE -F OCK, 503–510 total angular momentum, 449
equations, 506, 508 vector diagram, 451
restricted, 504 volume shift, 475, 477
unrestricted, 504 I
He atom, 22, 59, 341–375 Identity matrix,
1, 99
0th order approximation, 346–348 Independent particle model, 345, 355, 496, 497
diffraction, 59 Index of refraction, 57, 62, 400, 420–422
electron exchange, 351–355 Induced transitions
excited states, 351–360 dipole approximation, 189, 190
G ROTRIAN diagram, 343 probability, 215, 216
Insertion device, 540 L AMBERT-B EER law, 18, 178, 524

Intensity, 34, 632, 633 L ANDÉ g factor, see gJ factor
cycle averaged, 632 L ANDÉ’s interval rule
Intensity spectrum, 648, 649 fine structure, 308
Intercombination lines hyperfine structure, 452
forbidden in He, 363 L ANGEVIN function, 396
Interference, 89, 90 L ANGMUIR -TAYLOR detector, 75, 317
Interferometer, 278–281 L APLACE expansion, 613
FABRY-P ÉROT, 279–281 L ARMOR frequency, 72, 77, 79, 331, 485
free spectral range, 279 Laser based X-ray sources, 543, 544
opitcal path difference, 279 Lattice plane, 40, 42, 59
optical path difference, 278 L EGENDRE polynomial, 563
resolving power, 278 associated, 111
Interval rule, see Fine structure Leuchtelektron (valence electron), 144
Invariant mass, 10 Level splitting, 130
Ion beam spectroscopy, see Spectroscopy Li atom, 146
Ion cyclotron resonance G ROTRIAN diagram, 145
Spectrometer, 54 Light quantum, 27
Ionization Light scattering, 427–432
above-barrier, 436 coherent, 430
non-sequential, double, 438 C OMPTON, 430, 431
Ionization potential, 27, 75, 142, 146 from relativistic electrons, 431
of alkali atoms, 147 incoherent, 431
IR spectral range, 37 M IE, 427
Irradiance, 34 R AYLEIGH, 428, 429
Irreducible representation T HOMSON, 429
rotation group, 560, 575, 606 Light storage, 281
tensor operator, 560 Light year, 6
Limits of classical physics, 87
J Line broadening, 227–238
jj coupling, see Coupling, 513 by finite measuring time, 288
K homogeneous, natural, 231, 232
K shell, 139, 151 inhomogeneous, 236
K ELDYSH parameter, 434, 436 Lorentzian linewidth, 234
Kinematic correction, 68, 119, 321, 323, 474 Line spectra, 2
Kinetic gas theory, 18–20 Line strength, 212, 636, 637
K IRCHHOFF’s diffraction theory, 60, 89 Line triplet, 130
K LEIN -G ORDON equation, 93 ‘normal’ Z EEMAN effect, 131
KOHN -S HAM Liquid drop model for nuclear radius, 476
equations, potential, orbitals, 510 Long range potentials, 414
KOOPMAN’s theorem, 509 induced dipole – induced dipole, 417, 418
monopole – induced dipole, 416
L monopole – monopole, 414
L shell, 139, 151 monopole – permanent dipole, 415
L AGUERRE polynomials, 121 monopole – quadrupole, 415
L AMB dip, 286 permanent dipole – induced dipole, 416
L AMB shift, 316 permanent dipole – permanent dipole, 415
1st order perturbation theory, 328 quadrupole – quadrupole, 416
BALMER Hα, 316 L ORENTZ factor, 10
experiment of L AMB and R ETHERFORD, L ORENTZ force, 55, 295
317, 318 L ORENTZ profile, 229
highly charged ions, 322, 324 convolution, 628
optical precision spectroscopy, 319, 322 numerical examples, 231, 232
theory, 326, 331 LS coupling, see also Coupling, 512
LS interaction, see Spin-orbit interaction Mean free path length, 18

Lumen, 38 Mesons, 49
Luminous efficacy, 38 Metastable states of rare gases, 517
Luminous efficiency, 38 M ICHELSON interferometer, 278
photopic, 37 Microscope resolution according to Abbé, 62
Luminous flux, 38 M IE scattering, 427
Luminous intensity, 38 M ILLER indices, 41
Molar susceptibility, 395
M Molecular beam, 72, 282
Magic angle, see Photoionization resonance spectroscopy, 482–484
Magic angle spinning (MAS), see NMR M ØLLER -P LESSET perturbation theory, 498,
Magnet poles, 73 508
Magnetic dipole (M1) transition, 250–254, Momentum conservation, 429, 430
484, 488, 589, 590 F EYMAN graphs, 326
Magnetic field of the electron cloud, 453, 457 relativistic, 11, 30
Magnetic moment, 251 Momentum eigenfunction, 102
and angular momentum, 70, 71 Momentum operator, 91, 92
atomic nuclei, 447, 450 M OSLEY diagram, 160,161
in a magnetic field, 71, 72, 294, 295 Na-like ions, 160
of the electron, 331 X-ray absorption edges, 523
precessing in a magnetic field, 386, 388 Multi-electron atom, 344, 495–547
Magnetic resonance spectroscopy, 482–491 H AMILTON operator, 496–498
Magnetic susceptibility, 395
H ARTREE method, 500
diamagnetism, 397
self-consistent field method, 500, 501
paramagnetism, 396
with one valence electron, 144
Magnetization, 395
Multi-electron photoionization, 524–530
Magneton, 71
Multi-photon ionization, 244, 265–269
B OHR, 79, 129, 294
angular distribution of electrons, 266–269
Magnetron frequency, 332
kinetic energy of the electrons, 265
Main group
saturation, 434–436
periodic system of elements, 141
Mass absorption coefficient, 525 Multi-photon processes, 244–250
X-ray, 524 Multiple beam interference, 40
Mass correction Multiplicity, 76, 300, 302, 357, 363
relativistic, 54 Multipole expansion, 613–622
Mass polarization, 474 Multipole moment, 613–622
Mass selection, 53 Multipole tensor operator, 616–621
Mass spectrometer, 54–56 general, 619–621
double focussing, 55
quadrupole, 55 N
time of flight, 55 N atom, G ROTRIAN diagram, 515
Matrix eigenvalue equation, 164 Na atom, 149
Matrix element, 100, 116, 575, 592 electron density distribution, 150–152
angular momentum components, 586 radial electron density, 151
operator, 97 radial wave function, 149
reduction, 582–587 Natural lifetime, 229
spherical harmonics Natural linewidth, 227–229
LS-coupling, 583, 585 Natural unit of energy, 67
Matrix representation, 116 Ne atom, G ROTRIAN diagram, 517
Matter wave, 87–94 Neon shell, 151
plane, 58 Neutron, 48
M AXWELL’s equations, 92 Neutron diffraction, 59
M AXWELL -B OLTZMANN NIST data bank, 50, 118, 140, 146, 147, 157,
velocity distribution, 21, 72 159, 160, 166, 203, 259, 260, 309,
319, 342, 347, 349, 351, 371, 373, Nuclear quadrupole moment, 447, 449, 616
431, 514, 522, 525, 529, 551, 629 oblate or prolate, 478
NMR spectroscopy, 487–491 Nuclear radius, 29, 121
apparatus, 488 liquid drop model, 476
CW spectrum of ethanol, 488 Nuclear spin, 449
magic angle spinning (MAS), 490 eigenvalue equations, 449
occupation probability of levels, 489 Nuclear spin resonance, see NMR
N OBEL prize in chemistry Nucleons, 48
Richard R. E RNST (1991), 490
KOHN and P OPLE (1998), 510 O
F ENN, TANAKA, W ÜTHRICH (2002), 490 O atom, G ROTRIAN diagram, 516
N OBEL prize in physics Oblate, 477, 478, 619
Wilhelm C. RÖNTGEN (1901), 530 nuclear shape, 478
L ORENTZ and Z EEMAN (1902), 377 Observable, 97–99, 118
Joseph J. T HOMSON (1906), 50 commuting, 101
Albert A. M ICHELSON (1907), 278 non-commuting, 101
Max K. E. L. P LANCK (1918), 31 simultaneous measurement, 100, 101
Johannes S TARK (1919), 399 One electron cyclotron oscillator, 334
Albert E INSTEIN (1921), 27, 31 One particle problem, 117–134
Niels H. D. B OHR (1922), 64 One sided exponential distribution, 653
C ORNELL, K ETTERLE, W IEMAN (1925), One-loop QED effects, 323, 324
25 Operator, 96, 97, 100
Arthur H. C OMPTON (1927), 28 energy, 101
Louis DE B ROGLIE (1929), 57 momentum, 101
Werner K. H EISENBERG (1932), 100 position in space, 101
S CHRÖDINGER and D IRAC (1933), 90 simultaneous measurement, 101
Otto S TERN (1943), 70 Optical path difference, 40
Isidor I. R ABI (1944), 482 Orbital angular momentum, 71, 295, 299,
Wolfgang PAULI (1945), 22, 138 302
Max B ORN (1954), 88, 89 components, 110, 111
L AMB and K USCH (1955), 317 eigenfunctions, 109–113
T OMONAGA, S CHWINGER, F EYNMAN square, 111, 112
(1965), 79, 324, 534 Orbital energies, 509
R AMSEY, D EHMELT, PAUL (1989), 55, Orders of magnitude, 5–9
225, 288, 332, 482 energy scales, 7
G LAUBER, H ALL, H ÄNSCH (2005), 248, length scales, 5
319 time scales, 7
M ATHER, S MOOT (2006), 6, 7 Orthonormality relation, 96
E NGLERT and H IGGS (2013), 46 Oscillator strength, 238, 239, 636–640
N OBEL prize in physiology or medicine density, 256
L AUTERBUR, M ANSFIELD (2003), 490 sum rule, 239, 639, 640
Non-crossing rule, 391, 394
Non-local potential, 507 P
Non-stationary problems Pair production, 526
dipole excitation (E1), 169–225 Paramagnetism, 394–396
light matter interaction, 227–270 Parity, 593, 594
Non-stationary states, 186, 187 conservation in E1 transitions, 202
‘normal’ Z EEMAN effect, 128–131, 382–386 multi-electron systems, 594–603
Nuclear gN factor, 447, 449 Parity violation, 249
Nuclear magnetic moment, 447, 449, 485, 487, Particle detection, 75
488 Particle diffraction, 58–61
Nuclear magnetic resonance, see NMR C60 , 60, 61
Nuclear mass, 119 He atoms, 59, 60
energy correction, 68, 69 Particles and waves, 57, 64
Partition function, 21 P LANCHEREL’s theorem, 644

PASCHEN -BACK effect, see Z EEMAN effect, P LANCK constant, 4, 33
high field P LANCK energy, 9
PAUL trap, 332 P LANCK length, 5
PAULI spin matrices, 116 P LANCK time, 7
PAULI principle, 22, 138, 139, 351–355, P LANCK’s radiation law, 31–34
503–506 E INSTEIN’s derivation, 185
P ENNING trap, 332 Plane wave, 94
Periodic system, 137–144, 168 partial wave expansion, 661–663
table of elements, 140–144 Plasma frequency, 56, 57
Perturbation hierarchy Plasma oscillations, 56
with electric field, 402 Plasmon resonances, 57
Perturbation theory, 129 Pointing vector, 632
1st order, 162, 163 Polar coordinates, 107–110
2nd order, 163, 164 H atom, 117
alkali atoms, 165 Polarizability, 144, 150, 411–413
degenerate states, 164, 165 Polarization
stationary, 161–167 circular, 172, 173
time dependent, 186–196 dielectric, 411–413
1st order, 190 induced, 412
Phase diagram, 88 orientation, 412
Phase difference elliptical, 172–174
FPI interferometer, 280
linear, 171, 173, 174
Phase index, see Index of refraction
vector, 170–176
Phase shift
basis, 171–174
in QDT, 159
Polarization ellipse, 174
Phase space, 88
Polarization potential, 416
Phase velocity, 422–424
Ponderomotive potential, 432–434, 634,
Photo-absorption cross section, 42
635
aluminum, 525
Positron emission tomography (PET), 30
lead, 525
Photo-detachment, 255 Potential box
angular distribution of electrons, 264 one dimensional, 103, 104
Photoelectric effect, 26–28 three dimensional, 104–107
Photoelectron spectroscopy (PES), 28, 254, Potential well model, 27
268, 269 Power broadening, 230
imaging spectrometers (EIS), 268 Precession of angular momentum in a
Photographic plate, 59, 73, 74 magnetic field, 72
Photoionization, 254–269 Principle quantum number, 67
angular dependence, 260, 261 Probability amplitude, 87–90
anisotropy parameter, 260, 264 dependence on time, 92
Ar atom, 527 matter waves, 89, 90
B ORN approximation, 256–260 photon, 88, 89
cross section, 255–258 time dependent, 187
energy dependence, 259, 527–530 Probability distribution, 61, 89, 151
magic angle, 261 energy, 20
theory and experiment, 261–264 position, 123
with X-ray, 520, 524, 530 Probability interpretation, 89
Photometry, 37–40 Product ansatz, 93, 345
Photon, 4, 26–43, 62, 88–90, 92 Projection theorem for angular momenta, 578
angular momentum, 30, 175–198 Prolate, 477, 478, 619
elastic scattering, 527 nuclear shape, 478
flux, 179, 245 Proton, 48
momentum, 29 Proton radius, 7, 29, 324, 329
Q Rare gas, 142, 517

Quadrupole coupling constant, 481 no anions, 142
Quadrupole field, 55, 332 radii, 144
Quadrupole moment, 617–619 Rare gas configuration, 144
electric, 253 Rare gas shell, 139
intrinsic, 479 Rate equations, 184
spectroscopic, 479 R AYLEIGH criterium, 276
Quadrupole tensor R AYLEIGH SCATTERING, 428, 429
atomic nucleus, 478 Real solid harmonics
electric, 253 renormalized, 597
Quantization, 2–5 Real spherical harmonics, 596
Quantization of the electromagnetic field, 325 renormalized, 596
Quantum beats, 220–224 Reciprocal lattice vector, 40
Quantum defect, 146–148 Recollision, 438, 439
fine structure, 308, 309 Reduced mass, 119
He atom, 343 Reduced matrix element, 577
theory, 152–159 Reflection operator, 597, 617
Quantum electrodynamics (QED), 181, Reflection symmetry, 595–603
324–326 Relativity, see Special theory of relativity
Quantum jumps, 224, 225 Removal of degeneracy, 137–144
Quantum mechanics Removal of m degeneracy, 130, 131
axioms, 95–99 REMPI
definitions, 95–104 H atom, 1S–2S, 291
introduction, 87–134 Resolving power
representations, 99, 100 FABRY-P ÉROT interferometer, 280
Quantum number, 127 interferometer, 277
angular momentum, 77, 112, 138 Resonance denominator, 164
good, 121, 299, 595, 597, 599 Rest mass, 10
in a box, 104 Rotation group, 575
principle, 122, 123, 138, 139, 147 irreducible representation, 560, 606
projection, 76, 138 Rotation matrix, 606
spin, 78, 114, 138 Rule of D UANE -H UNT, 531
spin projection, 78 RUNGE -K UTTA method, 150
Quantum state, 95, 96 RUSSEL -S AUNDERS coupling, 512
Quasi-one-electron system, 144–161 RUTHERFORD, 65, 326
Quasi-two-electron system, 371–374 RYDBERG, 2
Quiver motion atoms, 253
high, oscillating field, 433 atoms and diamagnetic interaction, 398
atoms in electric fields, 409–411
R constant, 67, 69
Radial electron density constant, precision measurement, 321
computed with DFT, 511 states, 529
Radial matrix elements, 590, 592 RYDBERG -R ITZ formula, 69
Radial wave function, 166
Radian, 556 S
Radiance, 533 Saturation broadening, 230
spectral, 533 Saturation spectroscopy, see Spectroscopy,
Radiant flux, 34 D OPPLER free
Radiation Scalar product
spectral density, 33 of states, 95
spectral distribution, 31, 34 of tensor operators, 578
Radio frequency spectrum Scattering cross section, 326
lithium iodide, 483 S CHRÖDINGER equation, 90–92
R AMSEY fringes, 288, 289, 320, 484 alkali atoms, 149
H atom, 117 general concepts, 177, 178

stationary, 91 high resolution, 274–293
time dependent, 92–94 Spectrum
S CHRÖDINGER representation, 100, 107 He atom, 342
Screening Hg atom, 372
He atom, 343 visible, 34
of nuclear charge, 138 Spherical harmonics, 112, 113
Screening parameter, 153 matrixelements, 580–582
alkali like atoms, 159 products, 579
Na atom, 159 Spin
sech2 function, 651, 652 angular momentum, 99
convolution, 627 components, 115
Selection rules, 194 function, 301
Self adjoint operator, 97, see also Hermitian projection, 99, 140
operator Spin orientation and exchange interaction, 358
Self consistent field method, 498 Spin-orbit
Self-energy, 323 coupling, 568
S ELLMEIER equation, 420 coupling parameter, 296, 307, 378
Separation ansatz, 117 interaction, 293–303, 513
Shell closure, 142 splitting
Shell structure of atoms, 137–144 D IRAC theory, 306
Sinc function, 652 Spin-orbital, 503–508
Singlet function, 353 Spinor equation, 93
Singlet states, 301 Splitting of energy levels
Singlet system, 342 due to magnetic field, 130
Singlet transitions, 203 Spontaneous decay rate, 229
S LATER determinant, 358, 503–508 Spontaneous emission
Slow light, 422–427 and QED, 186
Solid harmonics, 616 E INSTEIN A coefficient, 183
Space quantization, 73–78 frequency dependence, 185
Special theory of relativity, 10–14 introduction, 181–183
and fine structure, 69 Spontaneous transition probability, 213, 214
L ORENTZ contraction, 13 Standard deviation, 15, 627
rest energy, 58 B OLTZMANN distribution, 235
rest frame, 13 Standard model, 4
time dilation, 13 of elementary particle physics, 46–48
twin paradox, 13 Standard phase convention, 563
Spectral brilliance, 534 S TARK states, 408
of various X-ray sources, 534 S TARK effect, 399–411
Spectral intensity distribution, 180 dipole states, 408
Spectral radiance, 34 dynamic, 418, 420
Spectral radiation density, 180 H(2s, 2p) states, 408
Spectrometer interaction potential, 400, 401
echelle, 277 linear, 407, 408
Spectroscopy matrix elements, 402
absorption, 177 high field, 403, 404
D OPPLER free low field, 404
ion beams, 283, 284 perturbation series, 405
microwave and RF transitions, 317 quadratic, 405, 406
molecular beams, 282, 283 RYDBERG atoms, 409–411
saturation, 285–288 significance, 399, 400
two-photon, 289–291 State of a quantum system, 95, 96
emission, 177 State vector, 95, 129
fluorescence spectroscopy, 177 States of a quantum system, 95
Stationary states, 176 Trajectory

Statistics classical, 87
classical, 20–26 Transition amplitude
elementary, 14–26 perturbation ansatz, 187, 189
quantum, 20–26 spherical basis, 198–200
S TEFAN -B OLTZMANN Transition matrix element
constant, 34 radial, 312
law, 34 Transition operator
Steradian, 554, 556 dipole approximation, 190, 635, 636
S TERN -G ERLACH experiment, 70–78, 99, Transition rate
114, 115 absorption, 191
interpretation, 75, 76 Transition rates in the continuum, 238
setup, 72, 73 Transmission grating, 60
Stimulated emission Trembling motion of an electron (so called
introduction, 180, 181 Zitterbewegung), 327
Strength of dipole transitions, 212–217 Triangular relation, 197, 201, 298, 565, 577
Strong force, 59 Triplet functions, 353
Structure analysis, 40–43 Triplet states, 301
Subgroup Triplet system, 342
periodic system of elements, 141 Tunnel ionization, 436, 437
Subshell, 142 Tunnelling effect, 75
Superluminal light propagation, 424–427 21 cm line, 460
Superposition principle, 89, 92 Two electron system, 341–375
Susceptibility, 413, 414, 420–422 Hamiltonian, 344, 345
Synchrotron radiation, 42, 53, 531–539 probabilities, 345
angle and energy dependence, 539 quantum mechanics, 344–351
critical wavelength, 538 Two level system
generation schematically, 537 thermodynamic equilibrium, 184
Two particle
T wave function, 345, 346
Tensor operator, 575–578 Two particle problem, 119
irreducible representation, 560 Two sided exponential distribution, 654
products, 578–582 Two wire field, 73
real, 595 Two-photon emission, 248, 249, 317
Term levels, see G ROTRIAN diagram Two-photon excitation, 245–248, 289, 320
Term scheme, see G ROTRIAN diagram H atom, 291
Terminology
of atomic structure, 301 U
Theory of special relativity Ultrafast physics, 8
rest energy, 67 Uncertainty relation
time dilation, 13 Gedanken-experiment, 61
T HOMAS -F ERMI equation, 502 H EISENBERG, 61, 63
T HOMAS -F ERMI potential, 501, 502 Undulator, 532
T HOMSON cross section, 527 Undulator and wiggler, 540–542
T HOMSON parabolas, 56 Unit operator
T HOMSON scattering, 429 quantum mechanics, 98, 99, 577, 583
nonlinear, relativistic, 543 Unit vector of polarization, 170
Time dependent density functional theory,
511 V
Time-bandwidth product, 651 Vacuum field, 181
Total angular momentum interaction of an electron with the,
eigenstates, 299–301 324
of the atomic charge could, 449 Vacuum polarization, 323
Total wave function, 138, 139 Vacuum-ultraviolet, 31
Valence electron, 75, 144, 146, 148 bremsstrahlung, 530

Na atom, 151 characteristic emission line, 521
VAN DER WAALS diffraction, 40–43
potential, 417, 418 sources, 530–544
radius, 142, 143 spectroscopy, 519–524
Variance, 15, 235, 626 AUGER electron, 522
Variational method, 350, 351 characteristic lines, 522–524
Vector boson, 44 M OSLEY formula, 522–524
Vector diagram, 78, 112, 129 X-ray tube, 530, 531
Vector model, 298, 381, 385
Vector operator, 91, 114, 576, 577 Y
Vector potential, 396, 631–634 YOUNG’s double slit experiment, 88
Velocity distribution, 285
Virial theorem, 66 Z
VIS, visible spectral range, 31 Z EEMAN effect, 9
VOIGT profile, 236, 237
‘normal’, 128–131
convolution, 628, 629
anomalous, 78
Volume term in HFS, 473
fine structure, 377–399
‘normal’, 382–386
W
anomalous, 379
Wave function, 88–96, 100, 104
symmetric and antisymmetric, 353 avoided crossings, 391
two particles, 345, 346 classical triplet in a high field, 386
Wave nature of matter, 58–63 examples, 382–384
Wave vector, 4, 13, 57, 94 high B field, 384–386
two-photon excitation, 289 interaction Hamiltonian, 377–380
Wave-packets, 88 intermediate field, 388–392
Wave-particle duality, 58, 61 limiting cases, 379, 392
Wavenumber, 31, 67 line strengths, 384
SI units, 31 low B field, 380–384
W EHNELT cylinder, 530 selection rule for transitions, 386
W IEN filter, 56 hyperfine structure, 461–471
W IEN’s displacement law, 34 B REIT-R ABI formula, 467–471
Wiggler, 532, 541, 542 ground state of 6 Li, 470
W IGNER -E CKART theorem, 576–578, 580, high B field, 464–466
582, 586, 617, 620, 621, 637 low B field, 462, 464
W IGNER -S EITZ radius, 143, 144 Na D lines, 464
transition to very high fields, 469
X Zero point energy, 181
X-ray Zero range potential, 436
absorption edge, 520, 521, 523 Zitterbewegung (trembling motion), 327
Index of Volume 2
Symbols Benzene
12, 6 potential, 149 D6h point group, 262
H ÜCKEL orbitals, 277–285
A β (anisotropy) parameter, 356, 360, 551, 557
A BBE sine law, 679 B ETHE formula, 528–530, 534, 537, 538, 546
Adiabatic representation, 478–480 ionization, 537
A IRY diffraction pattern, 25 B ETHE integral, 526
A IRY disc, 26 B ETHE ridge, 546, 548, 549, 553
Alignment, 596, 604, 616, 619, 698–700 B ETHE surface, 545
angle, 36, 44, 605, 610, 611 Binary peak in (e, 2e) process, 553
parameter, 622, 623, 698 Birefringence, 38, 40, 41
Alkali halide potentials, 220–224 B IRGE -S PONER plot, 177
Ammonia maser, 1, 252 Black body radiation, 105
Amplification profile, 15 B OLTZMANN
Amplified spontaneous emission, 11 distribution, 155, 173, 335, 389, 591
Anharmonicity constant, 162 statistics, 158
Anti-S TOKES lines, 334 Bond order, 195
Anti-symmetrization, 521 Bonding orbital, 183
Antibonding orbital, 183 B ORN approximation
Ar2 TPES spectrum, 369 first order, elastic, 444–448
Arn clusters, 400 generalized oscillator strength (GOS),
Atomic form factor 530–534
inelastic, 527 inelastic collisions, 460, 461, 522, 525–530
AUGER electron, 533 integral inelastic cross sections, 534
AUTLER -T OWNES effect, 637–639 B ORN phase shift, 447
Autocorrelation function, 53–60 B ORN series, 553
Avoided crossing, 220–224, 263 B ORN -O PPENHEIMER approximation,
139–151
B collision processes, 458, 474
Baseline in interferometry, 87, 91 BPP, see Beam parameter product
Beam divergence, 21, 22 Branching ratio, 653
Beam parameter, 17–21
product, 26, 34, 35 C
Beam radius, 17–35, 650 C6 H +
4 absorption spectra, 328
Beam waist, 17–21 C2 DFWN spectrum, 354
and coherence volume, 87 Carrier envelope, 46
and lateral coherence radius, 91 phase, 46, 55, 188

Carrier frequency, 45 Collision channels, 474

C ASIMIR operator, 541 Collision frame, 421, 422, 473
C AUCHY-S CHWARZ inequality, 83 Collision process
Cavity quantum electrodynamics, 127–130 elastic, 383–451
Cavity ring down spectroscopy, 327, 328 highly charged ions, 499–506
CCD camera, 315, 508, 676, 701 and ultrafast dynamics, 506
Centre of mass system, 389, 395, 396 inelastic, 453–513
Ceratron, 675 introduction, 383–393
CH4 , electronic states, 273 kinematics, 396–400
Channeltron, 674 COLTRIMS, 414, 501, 504, 685
Character tables, 257–262 Complex beam parameter
C2v , 258, 259 Gaussian beams, 19
Cs , 259 Confocal parameter in Gaussian beam, 21, 30
D2h , 260 Conical intersection, 263, 312, 323, 332, 507
D3h , 322 Conical skimmer, 321
D6h , 278, 279 Convergent close-coupling, 460, 464
Oh , 260–262 Correlation diagram, 192–194, 217
Td , 273 Correlation function, 52–60
Characteristic equation, 180 1st order, 72, 74
Charge exchange higher order, 55–58
H+2 system, 184–190 interferometric measurement, 54–58
H+ + H, 185–188 examples, see also Convolution
highly charged ions, 504, 505 C OULOMB integral, 182
over-the-barrier model, 501–503 Coupling elements
Chemical shift, 358, 360
non-adiabatic, 486, 487
Chemical-potential, 106
Cross section
Classical rainbow, 403
differential, 393–402
Classical trajectory, 402
integral, 394
Classical turning point, 406
momentum transfer, 395
Close-coupling
total, 385–387
convergent calculations (CCC), 522, 524,
Cusp in the e + He excitation, 464
529, 538, 539, 547, 548, 551, 553
Cytosine
theory, 460, 461, 516–519, 521, 523
Clusters photoelectron spectroscopy, 360
mass selection, 400–402
supersonic molecular beams, 321 D
CO D E B ROGLIE
nuclear spin statistics, 156, 157 wavelength, 402
CO2 Decay of coherence (T2 ), 641
infrared spectrum, 245 Decay of excitation (T1 ), 641
laser, 245 Degenerate four wave mixing (DFWM), 351
normal modes, 244, 245 Degree of coherence, 601, 602
Coherence, 72–100 1st order, 72
and incoherence, 580 2nd order, 84
angle, 90 N th order, 82
area, 91 Degree of polarization, 601, 602
length, 76, 78–82 coherence, 585–588
spatial, 86–91 linear, 43
time, 43, 76, 77, 79, 82, 84, 598 Degree of temporal coherence
volume, 91 2nd order, 82
Coherent anti-S TOKES R AMAN spectroscopy Delay line, 52
(CARS), 351 Density functional theory, 211
Coherent S TOKES R AMAN spectroscopy Density matrix, 573–624
(CSRS), 351 1 P state, 602–611
optical excitation, 609–623 of Hg, 466–468

transformation, 585 of molecules, 468, 469
Density of states of rare gases, 465, 466
photons, 105 Electron impact ionization, 534–562
Density operator, 581, 582 at threshold, 540–544
Depletion spectroscopy, 321 double-differential cross section, 544–549
Detailed balance, 387–389 GOSD, 545
Diabatic representation, 480–483 integral cross section, 537, 538
Diatomic molecules, 135–228, see also L OTZ formula, 537
Molecules, diatomic, 229 single-differential cross section, 539, 540
Dielectronic recombination, 563, 564 triple-differential cross section, 549–558
Differential cross section, 393–402 WANNIER threshold law, 542–544
Diffraction Electron jump
F RAUNHOFER, 23–26, 89, 413, 414 in ion molecule reactions, 221
F RESNEL factor, 25 Electron momentum spectroscopy, EMS,
F RESNEL number, 8, 20, 25 558–561
H UYGEN -F RESNEL principle, 23 Electron photo-detachment, 364
Dipole moment Electron scattering theory, 515–525
of a diatomic molecule, 167 Electronic spectra of molecules, 305–317
Dipole transition, 166–178 classical spectroscopy, 314–317
matrix element, 305, 480 laser induced fluorescence (LIF), 317–320
diatomic molecule, 167 laser spectroscopy
polyatomic molecules, 242 biomolecules, 328–333
operator, 119, 612 REMPI laser spectroscopy, 320–327
rotational transitions, 312, 313
Direct excitation process, 482
selection rules, 309–311
Directional intensity, 680
Electronic states
Dissociative ionization, 363, 366, 558
NH3 , 274, 275
Distorted wave approximation, 547, 553
of conjugated organic molecules, 277–285
Double resonance spectroscopy, 295, 330
triatomic molecules, 266–277
Dressed states, 629, 630
Ellipsoid of inertia, 232
coupled systems, 633–635
Ellipticity angle, 36, 44, 597
three, 659
Emission
D UNHAM coefficients, 165, 166 in a narrow band laser field, 635–639
DYSON orbital, 559 Energy defect
charge exchange, 501
E Energy imaging, see Velocity map imaging
e− rare gases Energy selector
integral elastic cross section, 392 hemispherical, 680–683
(e, 2e) process, 534 magnetic bottle, 683–685
Effective potential, 152, 163, 406, 413, time of flight method, 683–685
453–455 Entanglement, 575, 608
Effective range expansion, 430 Ergodicity, 75, 598
Eikonal approximation, 425 ESCA, 355–383
Elastic scattering, 383–451 Ethylenfluoroacetat, 361, 362
classical theory, 402–418 Exchange
Electric field and photon number, 116, 117 amplitude, 519
Electron and ion optics, 673–685 cross section, 519
Electron configuration, 141, 195, 205, 217, integral, 182
226, 259, 261, 263, 264, 267 symmetry, 156
Electron impact excitation electrons, 203
GOS (for e− Na), 533, 534 Excitation
of He, 461–463 continuous, with relaxation, 648, 649
fine details, 464 continuous, without relaxation, 647, 648
narrow band vs. broad band, 645, 646 R AYLEIGH length, 19

with short laser pulses, 649–652 Gaussian profile, 20, 59, 83, 644, 651
Excitation function, 459, 460–472 Generalized oscillator strength
density (GOSD), 545–549
F (GOS), 530–534
FABRY-P ÉROT resonator, 4–6, 50 Genetic algorithm, 332
FANO lineshape, 441 G LAUBER approximation, 553
FANO -M ACEK theory, 611–623 G LAUBER states, 114–117, 596
Fast and slow axis, 38 Glory oscillations, 391, 412
Femtochemistry, 507 Glow bar, 297
Femtosecond spectroscopy, 224 G OUY phase, 20
F ERMI resonance, 244
F ESHBACH resonance, 437 H
Field envelope H + He, integral elastic cross section, 390
phase of, see Carrier envelope phase H2
Field quantization and transitions, 110–131 MO ansatz, 206–210
Fine structure nuclear spin statistics, 156, 157
in H UND’s case (a), 200 ortho and para hydrogen, 156
Fluence, 49 potentials, 208, 209
FORT trap, 626 reflection symmetry, 203, 204
F ORTRAT diagram, 314 valence bond theory, 210, 211
F OURIER transform H+2 MOs, 181–184
limited pulses, 46, 47 H2 O
spectroscopy, 170, 293 absorption spectrum, 269
F OURIER transform spectroscopy, 298–302, C2v group, 258
343 electronic states, 266–270
of H2 O in the visible, 247 orbitals (EMS), 561
Fragment spectroscopy photoelectron spectroscopy, 358–360
KETOF, 364 rotational levels, 237, 238
MATI, 364 structure, 237
F RANCK -C ONDON vibrational spectrum, 245–247
factor, 305–312 H∗2 , predissociation, 207
principle, 306–309 Half wave plate, 40
F RANCK -H ERTZ experiment, 467 H AMILTON operator
F RAUNHOFER diffraction, see Diffraction diatomic molecules, 137, 138
Frequency comb, 49–52 heavy particle collision, 396
F RESNEL rhomb, 40 relative motion, 397
Fringe spatial frequency Hanbury B ROWN -T WISS, 72
stellar interferometer, 91 experiment, 84–86
Frozen-core approximation, 560 Harmonic oscillator, 143–145
FTIR, see F OURIER transform spectroscopy He-He potential, 149
Helicity basis, 36, 37, 42, 596, 597, 602
G polarization vectors, 101
Gain narrowing, 11 H ELMHOLTZ -L AGRANGE relation, 679
Gas kinetic cross section, 389 Hemispherical capacitor, 680–683
G AUSS radius, 22 H ERMITE functions, 144
Gaussian beam, 17–35 H ERMITE polynomials, 144
beam waist, 19–32 Hessian matrix, 240
complex beam parameter, 19 Hindered pseudorotation, 324
divergence angle, 22 Hole burning, 14–16
intensity and power, 21–23 with IR and UV, 330
nonlinear processes in, 61–67 HOMO, 195
radius of curvature of the wave front, 19, HOOO
21, 30, 31 IR action spectrum, 302
microwave spectrum, 295 J EFFREYS -B ORN phase shift, 426, 448

H ÜCKEL method, 279–285 JWKB phase shift, 426, 427, 494
H UND’s coupling cases, 199–201
Hybrid orbitals, 219 K
double bonding, 275, 276 K type doubling, 237
LiH, 219 K-matrix, 475, 521, 522
σ bonding, 273, 274
sp 3 orbitals, 270–272 L
triple bonding, 276, 277 Laboratory frame, 396
Hyperspherical coordinates, 540–542 Lambda-doubling, 205, 206
Lambda-half plate, 40
I Lambda-quarter plate, 38–40
I2 studied by LIF, 318, 319 L AMBERT-B EER law, 386
Imaging methods, 357, 365, 367, 369, 370 L ANDAU -Z ENER formula, 489–492
Impact parameter, 402, 404, 405, 408–412, L ANGEVIN cross section, 454–457
421, 422 Laser, 1–17
Incoherence by collisional excitation, 606–609 amplifier medium, 9–11
Index of refraction basic principle, 3, 4
particle beams, 678–680 diffraction losses, 8
Inertia tensor, 232 history, 1, 2
Infrared spectroscopy, 296–305 longitudinal modes, 5, 16
action spectroscopy (IAS), 302–304 population inversion, 14–16
Integral cross section, 408, 409 rate equations, 12–14
Intensity correlation function, 626 stability diagram, 7
Intensity interferometry, 98 threshold condition, 11, 12
Interaction experiment transverse modes, 6–8
state selective, 590–596 Laser beam
Intercombination lines, 309 diameter, 22
Interference experiment, 78, 79, 87 M2 factor, 34, 35
spatial, 87 profile measurement, 34
YOUNG’s, 78 Laser pulse, 45–48
Interferometer frequency spectrum, 45–48
M ACH -Z EHNDER, 52 Gaussian temporal profile, 46
M ICHELSON, 52, 59, 78 highest intensities, 3
stellar, M ICHELSON, 91–95 measurement of ultrashort, 52–60
Internal conversion, 312 mode coupled, 50
Inversion frequency, 250 spatial and temporal profile, 49
Inversion symmetry, 183, 202, 203 time dependence of sech2 , 46
Inversion vibration ultrafast, 59
in NH3 , 247–252 Laser spectroscopy, 317–334
p toluidine, 294 LCAO, 179, 180
Ion imaging, 66, 67 L ENNARD -J ONES potential, 149
Ion velocity map, see Velocity map imaging L EVINSON theorem, 429, 432
Irreducible representation Li3
density matrix, 614, 687, 693 high resolution spectroscopy, 321–327
dipole operator, 311 potential surface, 323
of point groups, 257 Lifetime
excited molecular states, 306, 307, 312
J H2 O, 270
JABLONSKY diagram, 335 internal conversion, 656
JAHN -T ELLER natural, 631, 640, 644
effect, 237, 262–265, 321–323 photons in a resonator, 4–6, 8, 12, 14, 327,
theorem, 262 328
vibronic coupling, 265 rate equations, 653
resonance scattering, 523 diatomic, heteronuclear, 215–218

RYDBERG state, 563, 564 diatomic, homonuclear, 179–197
Light beam, 17 Molecular potential, 140
LiH potentials, 218–220 Molecular spectroscopy, 289–381
Line broadening Molecules
saturation, 643–645 diatomic, 135–229
Linewidth electron spin, 197, 198
homogeneous and inhomogeneous, 14–16 electronic energy, 138
natural, 9, 127–130 equilibrium distance, 136
L IOUVILLE equation, 639, 640 heteronuclear, 215–226
L IPPMANN -S CHWINGER equation, 418–420 rotational energy, 139
Lone pair (of electrons), 223, 267 total angular momentum states,
ammonia, 274 197–214
Longitudinal coherence, 80 total energy diagram, 291
L ORENTZ profile, 4, 9–11, 76, 77, 81, 91, 107, vibration, 160–163
127, 300, 301, 643, 645 vibrational and rotational constants, 154
resonance scattering, 439 polyatomic, 231–288
L OTZ formula RYDBERG states, 224
electron impact ionization, 537, 538 valence states, 224
LUMO, 195 M OLLOW triplet, 635–637
Momentum conservation, 554, 558
M Momentum imaging methods, see Velocity
Magic angle, 357 map imaging
Main axis of symmetry, 254 M ORSE potential, 145–147, 163
MALDI, 330 MOs, 179, 180, see Molecular orbitals
M ALUS’s law, 44 MOTRIMS, 508, 685
Maser Multi-mode states, 117, 118
microwave amplification by stimulated Multi-photon ionization, 67
emission of radiation, 1 Multiplicity, 197, 205, 214
NH3 , 252 Multipole moment, 690–692, 698–700
M ASSEY criterium, 457, 459, 479, 481, 488, Multipole tensor operator, 690–692
491
modifed, 461, 491 N
M ASSEY parameter, see M ASSEY criterium N2
Matrix isolation spectroscopy, 333 nuclear spin statistics for bosons, 347
Mean free path length, 386 potentials, 211, 212
Measurement R AMAN spectrum, 343, 344
state analyzer, 588–590 N2 + e− shape resonance, 524
state selector, 588–590 Na atom
theory of, 588–596 hyperfine transition, 695–697
Merged-beams experiment, 564, 565 Na+ + Na(3p), inelastic and super-elastic
M ICHELSON interferometer, 298 processes, 492–496
Micro reversibility, 388 Na + Hg
Microchannel plate, 675 integral elastic cross section, 391
Microwave spectroscopy, 292–296 Na+2 potentials, 493
Mode density, 105 Na3 REMPI spectroscopy, 321
Mode locking, 50 NaCl potentials, 221, 222
passive, 328 NaI potentials, 222–224
Mode synchronization, 50 Natural lifetime, 127
Modes, see Laser N EWTON diagram, 397, 398, 400, 401
Modes of the radiation field, 103 NH3 , umbrella mode, 248–252
Molecular beam (NH3 )n , FEICO spectra, 371
seeded, 321 NIST data bank, 147, 162, 168–170
Molecular orbitals NO potentials, 224–226
N OBEL prize in physics Optical-optical double resonance

F RANCK and H ERTZ (1925), 467 in Li3 , 325
Chandrasekhara V. R AMAN (1930), 334 Orientation, 616, 619, 698–700
Isidor I. R ABI (1944), 630 Orientation parameter, 698
Robert H OFSTÄDTER (1961), 385 Oscillations
B LOEMBERGEN, S HAWLOW, S IEGBAHN glory, 391
(1981), 2, 317, 355 rainbow, 411
R AMSEY, D EHMELT, PAUL (1989), 695 shadow scattering, 412–415
G LAUBER, H ALL, H ÄNSCH (2005), 49, S TÜCKELBERG, 494, 496–498
52, 72 symmetry, 415–417
H AROCHE and W INELAND (2012), 128 Oscillator strength
N OBEL prize in chemistry density, 545
Robert S. M ULLIKAN (1966), 258 Overlap integral, 181
Gerhard H ERZBERG (1971), 314
H ERSCHBACH, L EE, P OLANYI (1986), P
221, 507 P toluidine, microwave spectrum, 294
C URL, K ROTO, S MALLEY (1996), 242 Partial wave analysis, 391, 392, 418, 427, 428,
Ahmed H. Z EWAIL (1999), 224, 507 433, 434, 475, 476, 484, 516, 517,
F ENN, TANAKA, W ÜTHRICH (2002), 330 523, 592
Non-adiabatic coupling, 477 e− − He and e− − Ne, 431, 432
Non-crossing rule, 194 Partial wave expansion, 422–425, see Partial
Nonlinear spectroscopy, 348–355 wave analysis
basics, 349–353 Partial waves, 423
BOXCARS, 353 Partition function, 156, 173
four wave mixing processes, 352 PAUL trap, 333
Normal modes, 239–243 P ENNING trap, 333
asymmetric stretch, 243 P ERCIVAL -S EATON hypothesis, 617
bending vibrations, 244 Periodic boundary conditions, 103
symmetric stretch, 243 Periodic system
transitions between, 242, 243 diatomic molecules, 194–197
triatomic molecule, 245–247 Phase matching, 352
Nuclear spin statistics, 157, 343–348 Phase shift
population of rotational levels, 155–157 scattering, 423
Nuclear wave function, 142, 143, 151–161 Phosphorescence, 311
Number operator, 111 Photo-dissociation
of H+2 , 188–190
O Photo-fragment spectroscopy, 333
O2 Photoelectron spectroscopy (PES), 355–372
H ERZBERG bands, 315, 316 anions, clusters, 364–366
nuclear statistics (bosons), 348 basics, 355–358
paramagnetism, 214 PEPICO, TPEPICO, 366–371
potentials, 211–213 PFI, 363
R AMAN spectrum, 344, 345 TPES, 363
reflection symmetry, 204, 205 ZEKE, 363
O5+ + e− Photoionization
dielectronic recombination, 563 anisotropy parameter, 356, 360
Oblate, 234–236, 699 magic angle, 357
Odd and even molecular orbitals, 183 Photomultiplier, 674
Optical B LOCH equations, 625–665 Photon
and short pulse spectroscopy, 649–657 introduction, 100–102
Optical multi channel analyzers, 316 modes of the radiation field, 102–105
Optical pumping, 626, 695–702 number per mode, 106–108
with two frequencies, 700–702 photon states, 100–108, 110
Optical theorem, 425 Photon annihilation operator, 113
Photon bunching, 84 Pulse train, 50

Photon creation operator, 113 Pure state, 577
Photon number states, 110–114 Pyrazine
Photon spin, 101 ZEKE and MATI spectra, 365
π pulse, 648
P LANCK’s radiation law, 106 Q
Plane wave impulse approximation, 559 Q factor of a resonator, 4
PN emission spectrum, 314 QED
P OCKELS cell, 41 cavity, 127–130
P OISSON distribution, 116 Quality factor of a resonator, 4
Polarizability, 337 Quantum beats, 617
Polarization, 35–45, 611 Quantum optics, 72–134, 626
analyzer for linear, 44 Quantum system
circular, 38, 40, 44, 101, 155, 596, 597, 609 in electromagnetic field, 639–642
degree of, 42, 43, 356, 580 temporal evolution, 639
density matrix for, 596–602 Quarter wave plate, 38–40
elliptical, 36 Quasi-monochromatic light, 43, 45, 75–77
field induced, 349
incomplete, 41–44 R
lambda-half plate, 40 R-matrix theory, 443, 464, 472, 522, 529
lambda-quarter plate, 38–40 R ABI frequency, 630, 631
linear, 36, 38, 102, 154, 155, 189, 356, 495, non-resonant, 633
609, 695 resonant, 631
linear, elliptic, circular, 37 R ABI oscillation, 627, 648
measuring the degree of, 43, 44 Radial coupling
nonlinear, 350 collision induced transitions, 480
rotating the plane of linearly polarized Radiationless transitions, 311, 312
light, 40 Radiative corrections, 128
selection rule in electron impact excitation, Radiative recombination, 563
532 Rainbow
S TOKES parameter, 600 heavy particle collisions, 409–417
S TOKES vector, 43, 600 optical, 403–405
time dependence of intensity by, 36–38 rapid oscillations, 411
Polyatomic molecules supernumerary, 410
vibration, 239–253 R AMAN active transitions, 338, 341
Population inversion, 9, 14, 16, 252 R AMAN scattering
Potential differential cross section, 341
anharmonic, 147 graph, 339
diatomic molecules, 141 R AMAN spectroscopy, 334–348
hypersurface, see Potential surface classic interpretation, 337, 338
L ENNARD -J ONES, 149 experimental aspects, 342, 343
surface, 140, 141, 262, 263, 265, 269, principle, 334–337
506–509 quantum mechanical theory, 338–342
H atom as three body problem|(, 541, R AMSAUER minimum, 391, 431
542 Rate constant, 386
‘Mexican hat’, 323 Rate equations, 386, 646, 647, 653–657
VAN DER WAALS , 141, 148–150 Ray tracing, 26
Potential hypersurface, see Potential surface Ray transfer matrix, 26–29
Predissociation of H∗2 , 207 R AYLEIGH criterium
Principle moments of inertia, 232 resolution of optical instruments, 89
Prolate, 234–236, 699 R AYLEIGH length, 19, 29, 30, 32, 63, 65
Pseudo-states, 522 R AYLEIGH line, 334
Pseudopotential, 437 Rb atom, hyperfine transition, 626
Pseudorotation, 321–327 Reaction coordinate, 508, 509
Reaction microscope, 414, 508, 685 asymmetric (non-rigid), 295, 303

Reactions asymmetric (rigid), 236–239
absorbing sphere, 455 spherical (rigid), 234
without threshold, 453, 454 symmetric top (rigid), 234–236
Recoil peak in (e, 2e) process, 553 Ruby laser, 2
Recombination, 563–566 RUTHERFORD
Reduced cross section, 407, 408 scattering, 407, 446, 447, 528, 529, 539,
Reduced scattering angle, 407, 408 559
Reflection symmetry, 203 RYDBERG
Refraction states in molecules, 224
of particle beams, 678 RYDBERG -K LEIN -R EES method, 177, 178
Relative velocity, 187, 386, 387, 390, 397, 398,
400, 409, 509 S
Resolving power S-matrix, 434, 475, 487, 494, 521, 522
FABRY-P ÉROT interferometer, 5 S-triazine, R AMAN spectrum, 345
R AYLEIGH criterium, 26 Saturation broadening, see Line width
Resonances, 436–444 Saturation intensity, 643
autoionization, 436 Scattering, elastic, 383–451
electron scattering Scattering amplitude, 410, 418–420, 424, 426,
by molecules, 523–525 433, 434, 488, 494, 576, 592, 606,
He− , 441–443 669
F ESHBACH, 412 direct, 519
formalism, 438–443 first B ORN approximation, 525–527
in electron scattering inelastic, 475, 476, 517, 518
H−2 , 207 semiclassical, inelastic, 487, 488
N−2 , 211 Scattering cross section
O−2 , 214
differential
orbiting, 412 beam-gas experiment, 394
predissociation, 412, 436 crossed beam experiment, 395
shape, 412 elastic, 385
types, 436, 437 elastic, integral, 389–392
Resonant capture, see Resonances, orbiting inelastic, 385
Resonator mode, 16 ionizing, 385
Resonator Q factor, see FABRY-P ÉROT reactive, 385
resonator total
Resonator quality factor, see FABRY-P ÉROT absorption experiment, 386
resonator Scattering kinematics, 396–400
Resonator turnaround time, 6 Scattering length, 429–431
Richtstrahlwert, 680 Scattering matrix, 432–435
Room temperature, 148 Scattering phase, 418
Rotating wave approximation, 123, 631–633 Scattering theory
Rotational constant, 155 classical, 405–409
diatomic molecules, 153 multi channel problem, 472–484
Rotational coupling phase shifts, 428–435
collision induced transitions, 480 quantum mechanical, 418–436
Rotational spectrum semiclassical, elastic, 425–428
CO, 168 semiclassical, inelastic, 487–489
Rotational temperature, 155 semiclassical approximation, 484–499
Rotational transitions, 167–170 S CHRÖDINGER equation
Rotor, diatomic molecules, 137
non-rigid, 163–165 sech2 function, 47
rigid, 152–157, 160–162, 200 Secondary electron multiplier, 673–678
Rotor, polyatomic, 231 Seeded molecular beam, 321
SF6 Sudden approximation, 560

Oh group, 261 Surface hopping, 312, 506–509
Shape resonance, 437 SVE approximation, see Slowly varying
Short pulse generation, 49–52 envelope approximation
σ ± light, see Polarization, circular Symmetry
Single atom in a MOT trap, 627 character tables, see Character tables
Single electron capture, 501 cylinder, 190
Slowly varying envelope approximation, 18, 42 g, u, 191
S OLEIL -BABINET compensator, 40 molecular physics, 253–265
sp 2 orbital point groups, 254–257
double bonding, 275, 276 reflection, 201–205
Spatial coherence
degree of, 89 T
Spatial filter, 33 T-matrix, 420, 433, 434, 475, 476, 487, 517,
Specific heat capacity, 158, 160 519, 521, 522, 592, 594
Spectrum inelastic scattering, 517
electromagnetic radiation for molecular Telescope systems
spectroscopy, 290–292 K EPLER and G ALILEI, 32, 33
Spontaneous line broadening, see Line Temporal coherence, 80
broadening, natural Tensor operator
Stability diagram statistical, 688
laser oscillation, 7 Tetrahedral angle, 272
Standard deviation Three body problem, 535, 541, 542, 555, 557
P OISSON distribution, 116 Threshold amplification, 14
S TARK effect, 171, 172 Threshold inversion, 14, 15
State multipole, 614, 687–694 Threshold laws, 470, 472
State of a quantum system Tight binding method, 285
coherent and incoherent, 579 Time-bandwidth product, 48
pure and mixed, 575–581 Toroidal energy analyzer, 556
State selection, 577 Transition
Stationary phase, 426–428 field quantization, 110–131
Statistical tensor, 687–694 L ANDAU -Z ENER, 489–492
operator, 688 non-adiabatic, 477, 478
Statistics perpendicular, 245
B OLTZMANN, 389 Triatomic molecules
exponential distribution, 76 linear, 243–245
of coincidence methods, 560 nonlinear, 245–247
Tunnelling
of measurement, 368
in predissociation, 207
quantum, 72
level splitting in NH3 , 247–252
Stellar interferometer
Two level system, 119, 629–635
Hanbury B ROWN -T WISS, 95–98
excitation with CW light, 642–649
Stimulated emission pumping, 658
STIRAP, 657–665 U
energy splitting and evolution of states, Ultrafast laser pulses
659, 660 measurement, interferometric, 60
experiments, 661–665 Ultrashort light pulse, see also Correlation
three level system, two laser fields, function
657–659 Unimolecular dissociation, 321
S TOKES lines, 334
S TOKES parameters, 41, 42, 596, 598–600, V
602 Valence states
experimental determination, 600, 601 in molecules, 224
S TOKES shift, 308 Van C ITTERT-Z ERNICKE theorem, 89
S TOKES vector, 42, 600 VAN DER WAALS
contact distance, 149 polyatomic molecules, 253

equation, 148 Vibronic coupling, 262, 265, 321–327
potential, 148–150, 409 Visibility, 80
radius, 150 VMI, see Velocity map imaging
Variational method, 179, 180
R ITZ, 208 W
Velocity WANNIER ridge, 542, 556
of electrons and atomic nuclei, 136 WANNIER threshold law, 470, 542–544
Velocity map imaging (VMI), 66, 67, 188, 357, Wave equation, 17
384, 507, 508, 676–685 general case, 350
Vertical binding energy, 358 Wave-packets, 45–52, 82
Vertical ionization potential, 358 Whole burning spectroscopy, 330
Vibration-rotation spectra, 174–177 W IGNER -E CKART theorem, 615, 671, 687,
CO, 174 688, 691, 699
PQR branches, 175 WKB phase shift, 426, 448
Vibrational quantum number, 152
Vibrational transitions Z
diatomic molecules, 172, 173 Zero point energy, 112, 145
in polyatomic molecules, 242 C60 , 242

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Appendices

A.1 Fundamental Physical Constants and Units

Modern physics relies on the knowledge of a relatively large number of so called

© Springer-Verlag Berlin Heidelberg 2015 551

Table A.1 (Continued)

Table A.1 (Continued)

A.2 SI and Atomic Units

• standard prefixes (NIST, 2000b), e.g. cm, mg, fs,

r/a0 , t/t0 , and W/Eh , respectively, (A.1)

A.3 SI and GAUSS Units

A.4 Radian and Steradian

Fig. A.1 On the definition of (a) radian and (b) steradian

A.5 Dimensional Analysis

• make a first check on the validity of a physical expression,

Throughout these textbooks we frequently make use of these possibilities. Thus, we

1. Physical quantities, such as the electron mass typically have

• a symbolic name, such as “me ”,

• a unit, here “kg”.

Acronyms and Terminology

AMO: ‘Atomic, molecular and optical’, physics.

B.1 Angular Momenta

B.1.1 General Deﬁnitions

The generalized angular momentum operator J is defined as vector operator with

Ji† = Ji for i = x, y, z, (B.1)

which satisfy the commutation relations

© Springer-Verlag Berlin Heidelberg 2015 559

J+† = −J− and J−† = −J+ , (B.5)

and their commutation relations are derived from (B.2):

[J0 , J± ] = ±J± and [J+ , J− ] = −J0 , (B.6)

in accordance with the general definition of scalar products of tensor operators

J0 J± |J M = J± J0 |J M ± J± |J M

With (B.7) the new states J± |J M are also eigenfunctions of

Equivalently one may write:

B.1.2 Orbital Angular Momenta – Spherical Harmonics

Pm (x) are the associated L EGENDRE polynomials

which in turn are derived from the ordinary L EGENDRE polynomials

We also note the orthogonality relation

With P0 (cos θ ) = 1 follows for all L EGENDRE polynomials with  > 0

and inversion at the origin (r → −r) leads to

Ym (π − θ, π + ϕ) = (−1) Y−m (θ, ϕ). (B.27)

We note the special values

Explicit expressions for the renormalized spherical harmonics up to  = 3 are given

Table B.1 Spherical harmonics according to (B.28) and (B.29)

2 0 d0 62 0 C20 = 12 (3 cos2 θ − 1)

3 0 f0 122 0 C30 = 12 (5 cos3 θ − 3 cos θ)

B.2 Coupling of Two Angular Momenta: CLEBSCH-GORDAN

When coupling two angular momenta

2. for the projection quantum numbers Mi = M1 , M2 and M

−Ji , −Ji + 1, . . . ≤ Mi ≤ Ji and (B.35)

B.2.2 Orthogonality and Symmetries

The following orthonormality relations hold:

Correspondingly, the 3j symbols satisfy the orthogonality relations:

The 3j symbols are symmetric in respect of cyclic exchange of their columns.

B.2.3 General Formulae

with the so called triangular function

(a + b − c)!(a − b + c)!(−a + b + c)!

B.2.4 Special Cases

From (B.45) one finds the rule:

A rather compact expression is also obtained if S = J1 + J2 + J is even and all

Frequently used relations are:

B.3 RACAH Function and 6j Symbols

|j1 m1 |j2 m2 |j3 m3  = |j1 m1 j2 m2 j3 m3 

in an uncoupled representation. Formally, the total angular momentum vector oper-

J0 J± |J M = J± J0 |J M ± J± |J M

With (B.7) the new states J± |J M are also eigenfunctions of

Pm (x) are the associated L EGENDRE polynomials

With P0 (cos θ ) = 1 follows for all L EGENDRE polynomials with > 0

Ym (π − θ, π + ϕ) = (−1) Y−m (θ, ϕ). (B.27)

Explicit expressions for the renormalized spherical harmonics up to = 3 are given

|j1 m1 |j2 m2 |j3 m3 = |j1 m1 j2 m2 j3 m3

from which with |j3 m3

where we have simply inserted the quantum mechanical unit operator

We recall that this expression is zero if + k + is odd. We also note that

and more generally for = one obtains with (B.50)

parity conservation holds: = ± 1 (C.35)

This expression is only non-zero if + + k is even. Thus, (C.45) reads now

This expression is even independent of and (of course + + k must be even)