Polarizabilities

Patrick Norman

Department of Physics, Chemistry and Biology

Linköping University

Virginia Tech, June 29–July 3, 2015

Topics for our discussion

We will discuss:
I Response functions for linear and nonlinear optics
I Molecular property tensor symmetries
I Optical responses in wave and corpuscular views of light
radiation
I Dispersion relations for property tensors
I Molecular and laboratory coordinate frames

Our considerations are general and apply to exact as well as

approximate state theories.
Linear Optics

The degree to which the external field F (t) manages to set the
charges in motion is, to first order, expressed in terms of the linear
electric polarizability α.
In linear optics, the time-dependent polarization is described with
an expression such as

µ(t) = µ0 + αF (t)

where µ0 is the permanent electric dipole moment of the molecule.

The polarizability tensor is available from our theory in the form of
a linear response function

ααβ (ω) = hhµ̂α ; −µ̂β iiω

Nonlinear Optics
In nonlinear optics, a generalization of the polarization is
introduced in terms of a Taylor series in the electric field
1 1
µ(t) = µ0 + αF (t) + βF 2 (t) + γF 3 (t) + · · ·
2 6
This equation introduces the first-order (nonlinear)
hyperpolarizability β, the second-order hyperpolarizability γ, and
so forth.

Historical remarks:
I The name hyper polarizability was given due to the presumed increase in
the linear polarizability for systems in strong electric fields.
(hyper: above)
I The name hypopolarizability was suggested for systems were there was a
decrease in the linear polarizability, but it has not entered into common
circulation. (hypo: under)

C.A. Coulson, A. Macoll, L.E. Sutton, Trans. Faraday Soc. 48, 106 (1952).
More recently as due to T. Saue

Hyper-Polar-Ice-Ability
Fourier decomposition of electric field

Fαω e −iωt
P
Fα (t) = ω

This yields:
X
µα (t) = µ0α + ααβ (−ω; ω)Fβω e −iωt
ω
1 X
+ βαβγ (−ωσ ; ω1 , ω2 )Fβω1 Fγω2 e −iωσ t
2 ω ,ω
1 2

1 X
+ γαβγδ (−ωσ ; ω1 , ω2 , ω3 )Fβω1 Fγω2 Fδω3 e −iωσ t + · · ·
6 ω ,ω ,ω
1 2 3

where ωσ denotes the sum of optical frequencies: for terms

involving β then ωσ = (ω1 + ω2 ) and for terms involving γ then
ωσ = (ω1 + ω2 + ω3 ). The Einstein summation convention for
repeated subscripts is assumed here and elsewhere.
Tensor relations regarding frequency sign

X
µα (t) = µ0α + ααβ (−ω; ω)Fβω e −iωt + . . .
ω

Since the molecular polarization µ(t) as well as the electric field

F (t) are real, we have

α(ω; −ω) = [α(−ω; ω)]∗

β(ωσ ; −ω1 , −ω2 ) = [β(−ωσ ; ω1 , ω2 )]∗
γ(ωσ ; −ω1 , −ω2 , −ω3 ) = [γ(−ωσ ; ω1 , ω2 , ω3 )]∗
Tensor intrinsic symmetries

X
γαβγδ (−ωσ ; ω1 , ω2 , ω3 )Fβω1 Fγω2 Fδω3 e −iωσ t
ω1 ,ω2 ,ω3

I We note that any pairwise interchange of the indices and

frequencies {β, ω1 }, {γ, ω2 }, and {δ, ω3 } can be made
without altering the physically observable polarization µ(t).
I It is therefore customary, but not necessary, to demand that
the individual tensor elements are intrinsically symmetric

βαβγ (−ωσ ; ω1 , ω2 ) = βαγβ (−ωσ ; ω2 , ω1 )

γαβγδ (−ωσ ; ω1 , ω2 , ω3 ) = γαβδγ (−ωσ ; ω1 , ω3 , ω2 )
= γαγβδ (−ωσ ; ω2 , ω1 , ω3 ) = γαγδβ (−ωσ ; ω2 , ω3 , ω1 )
= γαδγβ (−ωσ ; ω3 , ω2 , ω1 ) = γαδβγ (−ωσ ; ω3 , ω1 , ω2 )
Tensor overall symmetries

In the nonresonant regions of the spectrum, the polarizabilities are

real valued, and the tensors possess overall permutational
symmetry:

βαβγ (−ωσ ; ω1 , ω2 ) = ββαγ (ω1 ; −ωσ , ω2 )

γαβγδ (−ωσ ; ω1 , ω2 , ω3 ) = γβαγδ (ω1 ; −ωσ , ω2 , ω3 )
= γγβαδ (ω2 ; ω1 , −ωσ , ω3 ) = γδβγα (ω3 ; ω1 , ω2 , −ωσ )
Example I: bichromatic laser

−ωA −ωB ωB ωA
Let two lasers A and B, which operate at frequencies ωA and ωB ,
respectively, interact. The external electric field experienced by the
molecular system will in this case become

Fα (t) = FαωA cos(ωA t) + FαωB cos(ωB t)

Including terms up to second-order in the field, the time-dependent

polarization will be

µα (t) = µ0α + ααβ [FβωA cos(ωA t) + FβωB cos(ωB t)]

1
+ βαβγ [FβωA cos(ωA t) + FβωB cos(ωB t)][FγωA cos(ωA t) + FγωB cos(ωB t)]
2
Induced polarization

cos u cos v = 12 [cos(u + v ) + cos(u − v )]

X
µα (t) = µ0α + ααβ (−ω; ω)Fβω cos(ωt)
ω={ωA ,ωB }

1 1
+ βαβγ (0; ω, −ω)Fβω Fγω + βαβγ (−2ω; ω, ω)Fβω Fγω cos(2ωt)
2 2
+ βαβγ (−(ωA + ωB ); ωA , ωB )FβωA FγωB cos([ωA + ωB ]t)
+ βαβγ (−(ωA − ωB ); ωA , −ωB )FβωA FγωB cos([ωA − ωB ]t).
Nonlinear Optical Processes

I Second-harmonic generation: 2ωA and 2ωB

I Sum-Frequency Generation: (ωA + ωB )
I Difference-Frequency Generation: (ωA − ωB )
Wave–particle duality
Light can either be considered a classical electromagnetic wave or
as a stream of photons and both pictures are useful to understand
linear and nonlinear optical phenomena.
Difference-Frequency Generation

|1i
∆E

ωB
ωA

(ωA − ωB )
|0i
I The light quanta of frequency ωA is annihilated and those of frequencies
ωB and (ωA − ωB ) are both created (two-photon emission).
I The creation of the photon with frequency ωB is a result of stimulated
emission induced by laser B.
I It is thus in principle possible to amplify a weak light signal B with a
pump laser A.
Example II: monochromatic laser and static field

Fα (t) = Fα0 + Fαω cos(ωt)

µα (t) = µ0α + ααβ [Fβ0 + Fβω cos(ωt)]

1
+ βαβγ [Fβ0 + Fβω cos(ωt)][Fγ0 + Fγω cos(ωt)]
2
1
+ γαβγδ [Fβ0 + Fβω cos(ωt)][Fγ0 + Fγω cos(ωt)][Fδ0 + Fδω cos(ωt)].
6
Re-write on form:

µα (t) = µ̃0α + µ̃ω 2ω 3ω

α cos(ωt) + µ̃α cos(2ωt) + µ̃α cos(3ωt),

We then get...
 1
µ̃0α = µ0α + ααβ (0; 0)Fβ0 + βαβγ (0; 0, 0)Fβ0 Fγ0
2
1
+ γαβγδ (0; 0, 0, 0)Fβ0 Fγ0 Fδ0
6
1 1
+ βαβγ (0; −ω, ω)Fβω Fγω + γαβγδ (0; −ω, ω, 0)Fβ0 Fγω Fδω ,
4 4
µ̃ω
α = ααβ (−ω; ω)Fβω + βαβγ (−ω; ω, 0)Fβω Fγ0
1
+ γαβγδ (−ω; ω, 0, 0)Fβω Fγ0 Fδ0
2
1
+ γαβγδ (−ω; ω, −ω, ω, )Fβω Fγω Fδω ,
8
1
µ̃2ω
α = βαβγ (−2ω; ω, ω)Fβω Fγω
4
1
+ γαβγδ (−2ω; ω, ω, 0)Fβω Fγω Fδ0 ,
4
1
µ̃3ω
α = γαβγδ (−3ω; ω, ω, ω)Fβω Fγω Fδω .
24
We prefer Taylor expansions of the polarization

2ω
µ̃α = 14 βαβγ (−2ω; ω, ω)Fβω Fγω + 14 γαβγδ (−2ω; ω, ω, 0)Fβω Fγω Fδ0

An alternative summary of this result is sometimes expressed as an expansion

of the polarization amplitudes in terms of the electric field amplitudes
1 (2)
µ̃ω
α
σ
= α(−ωσ ; ω1 )F ω1 + K β(−ωσ ; ω1 , ω2 )F ω1 F ω2
2
1
+ K (3) γ(−ωσ ; ω1 , ω2 , ω3 )F ω1 F ω2 F ω3 + · · · ,
6
where the factors K (n) are required for the polarization related to the molecular
response of order n to have the same static limit.
Conversion factors

Process Frequencies Factor

Second-order processes K (2)
Static 0; 0, 0 1
EOPEa −ω; ω, 0 2
SHGb −2ω; ω, ω 1/2
Third-order processes K (3)
Static 0; 0, 0, 0 1
EOKEc −ω; ω, 0, 0 3
IDRId −ω; ω, −ω, ω 3/4
ESHGe −2ω; ω, ω, 0 3/2
THGf −3ω; ω, ω, ω 1/4

a
Electro-optical Pockels effect. b Second-harmonic generation. c Electro-optical
Kerr effect.d Intensity-dependent refractive index. e Electric field-induced second
harmonic generation. f Third-harmonic generation.
Dispersion of polarizability

 
1 X0 h0|µ̂α |nihn|µ̂β |0i h0|µ̂β |nihn|µ̂α |0i
ααβ (−ω; ω) = +
~ n ωn0 − ω ωn0 + ω

In the nonrelativistic limit, the unperturbed eigenfunctions of the

molecular Hamiltonian can be chosen as real and the numerators
of the two terms are then equal and can be separated out:

1 X0 2 h0|µ̂α |nihn|µ̂β |0i

ααβ (−ω; ω) =
~ n ωn0 1 − (ω/ωn0 )2
With use of the Taylor expansion
∞
1 X
= xk for |x| < 1,
1−x
k=0

we get ...
Cauchy moment expansion
∞
X
−1
ααβ (−ω; ω) = ~ ω 2k S(−2k − 2) for |ω/ωon | < 1,
k=0

where the Cauchy moments S(−k) have been introduced as

X0 f αβ αβ
n0
S(−k) = k
; fn0 = 2ωn0 h0|µα |nihn|µβ |0i.
n
ωn0

I The Cauchy moments are independent of the optical

frequency.
I The expansion of the polarizability in the optical frequency
contains only terms of even power.
I The Cauchy moments with α = β are positve, the dispersions
of the diagonal components of the polarizability are bound to
be positive.
Dispersion of hyperpolarizability
The dispersions of hyperpolarizabilities are considerably more
complicated, e.g.,

1 X X0 h0|µ̂α |nihn|µ̂β |pihp|µ̂γ |0i

βαβγ (−ωσ ; ω1 , ω2 ) = 2
P−σ,1,2
~ np
(ωn0 − ωσ )(ωp0 − ω2 )

where µ̂ is the fluctuation dipole moment operator µ̂ − h0|µ̂|0i.

If we first consider a diagonal component of the β-tensor, it is clear
that the frequency dependence rests in
 
X 1
P−σ,1,2
(ωn0 − ωσ )(ωp0 − ω2 )
 
∞  k  l
1 X X ω σ ω 2
= P−σ,1,2  
ωn0 ωp0 ωn0 ωp0
k,l=0
Auxiliary permutation formulas
 
∞  k  l
1 X X ωσ ω2
P−σ,1,2  
ωn0 ωp0 ωn0 ωp0
k,l=0

P P
We introduce the notaion of ω−σ = −ωσ as well as P−σ,1,2,...,n = P, and
get:
X
1 = (n + 1)!,
P
X n
X
ω1 = n! ωk = 0,
P k=−σ

X n
X
ω12 = n! ωk2 = n! ωL2 ,
P k=−σ

X n
X X
ω1 ω2 = (n − 1)! ωk ωl = −(n − 1)! ωL2 ,
P k=−σ l6=k

where ωL2 is defined by the above equation.

General dispersion formula for first hyperpolarizability

βzzz (−ωσ ; ω1 , ω2 ) = βzzz (0; 0, 0) + A ωL2 + ...

where the coefficient A has been introduced as

X0 T zzz
!
np 2 2 1
A = 2
+ 2 + ,
n,p
ωn0 ωp0 ωn0 ωp0 ωn0 ωp0

with

αβγ
T np = h0|µ̂α |nihn|µ̂β |pihp|µ̂γ |0i.
How to attract attention
ω (a.u.)
0 0.01 0.04
β(−ω; ω, 0) 8.4037 8.4085 8.4814
β(−2ω; ω, ω) 8.4181 8.6401

8.4085−8.4037
A≈ 2×0.012
≈ 24.0

βzzz (−0.04; 0.04, 0) = βzzz (0; 0, 0) + A (2 × 0.042 )

βzzz (−0.02; 0.01, 0.01) = βzzz (0; 0, 0) + A (6 × 0.012 )

βzzz (−0.08; 0.04, 0.04) = βzzz (0; 0, 0) + A (6 × 0.042 )

Needless to say, you are the center of attention after this...

First hyperpolarizability of hydrogen fluoride

-8.0
βzzz(−2ω;ω,ω)
-8.5 βzzz(−ω;ω,0)
βzzz

-9.0

-9.5

0.00 0.01 0.02 0.03 0.04 0.05

ωL2
-8.0

-8.5
βzzz

-9.0

-9.5

0.00 0.02 0.04 0.06 0.08

ω

Hartree–Fock/t-aug-cc-pVTZ results for SHG and EOPE optical processes.

The dipole moment is directed along the positive z-axis and the experimental
bond length of 1.733 a.u. is employed. All quantities are given in a.u.
General dispersion formula for first hyperpolarizability
1 X
γαβγδ (−ωσ ; ω1 , ω2 , ω3 ) = P−σ,1,2,3
~3
 
X0 h0|µ̂α |nihn|µ̂β |mihm|µ̂γ |pihp|µ̂δ |0i X0 h0|µ̂α |nihn|µ̂β |0ih0|µ̂γ |mihm|µ̂δ |0i
× − 
nmp (ωn0 − ωσ )(ωm0 − ω2 − ω3 )(ωp0 − ω3 ) nm (ωn0 − ωσ )(ωm0 − ω3 )(ωm0 + ω2 )

γzzzz (−ωσ ; ω1 , ω2 , ω3 ) = γzzzz (0; 0, 0, 0) + A ωL2

where the frequency-independent coefficient A is equal to

zzzz !
X0 T nmp 6 8 6 4 2 4
A = 2
+ 2 + 2 + + +
n,m,p
ω n0 ω m0 ω p0 ωn0 ω m0 ωp0 ωn0 ωm0 ωn0 ω p0 ωm0 ωp0
X T 0 zzzz 
6 14

nm
− 2 2
+ 2 ,
n,m
ω n0 ω m0 ω n0 ω m0

with
αβγδ
T nmp = h0|µ̂α |nihn|µ̂β |mihm|µ̂γ |pihp|µ̂δ |0i,
αβγδ
Tnm = h0|µ̂α |nihn|µ̂β |0ih0|µ̂γ |mihm|µ̂δ |0i.
Second hyperpolarizability of hydrogen fluoride

420

380
γzzzz

340

300
0.00 0.02 0.04 0.06 0.08 0.10
ωL2
420
γzzzz(−3ω;ω,ω,ω)
380 γzzzz(−2ω;ω,ω,0)
γzzzz(−ω;ω,−ω,ω)
γzzzz

340 γzzzz(−ω;ω,0,0)
300
0.00 0.02 0.04 0.06 0.08
ω

Hartree–Fock/t-aug-cc-pVTZ results for THG, ESHG, IDRI, and EOKE optical

processes. The dipole moment is directed along the positive z-axis and the
expt bond length of 1.733 a.u. is employed. All quantities are given in a.u.
Change of coordinate system

The polarizability in the laboratory frame is connected to that in

the molecular frame via
X
αAB (ω) = ααβ (ω) cos(A, α) cos(B, β),
αβ

where (A, α) denotes the angle between the laboratory axis A and
the molecular axis α.
Tensor averaging

Experimentally determined properties relate to laboratory axes. The connection

is made by taking classical orientational averages (in quantum mechanical
terms by taking into account rotation).
For hαiZZ , commonly referred to as α, if Z is a space fixed axis and kα is the
cosine of the angle between Z and the molecular axis α, we have

α = hαiZZ
Z 2π Z π
1 1
= ααβ kα kβ sin θdθdφ = (αxx + αyy + αzz )
4π 0 0 3
For hγiZZZZ , commonly referred to as γ, or γk , we have

γ = hγiZZZZ
Z 2π Z π
1
= γαβγδ kα kβ kγ kδ sin θdθdφ
4π 0 0
1
= (γξξηη + γξηξη + γξηηξ ).
15
Summary
I A corpuscular view of light radiation is benefitial for a rationalization of
optical processes.
I A wave view, on the other hand, is the starting point for definitions of
molecular properties.
I In nonresonant regions, polarizabilities are real valued and symmteric
w.r.t. an overall sign change of optical frequencies.
I We are free to require intrinsic symmetry of tensors w.r.t. pairs of optical
frequncies and perturbation operators.
I In nonresonant regions, tensors are overall symmetric.
I General dispersion formulas show that diagonal tensor elements and
isotropic averages have positive dispersion in the limit of nonoscillating
optical fields.
I Comparisons with experimental results for gases and liquids will involve
averaging (due to rotation) of tensor elements.
I In resonant regions of the spectrum, polarizabilities become
complex-valued with imaginary parts that are related to absorption of
photons by the molecular system.