Chapter 12 Linear Response Theory

12.1 A simple quantum mechanics problem

Let us rst consider a simple quantum mechanics problem: A hydrogen atom in a weak optical eld E(t). We wish to calculate the polarization of the atom d(t) in the rst order of E(t), and calculate some optical quantities such as absorption. In the atom, the nucleus is so heavy that we can regard it as motionless. The Hamiltonian of the atom without the optical eld is denoted as H0 . The eigenstates and eigenenergies are |n and n , respectively. The polarization of the atom (dipole) is thus totally determined by the position of the electron, i.e., d er. (12.1) Under the optical eld, the interaction Hamiltonian is V(t) = d E(t) = exE(t). (12.2)

Here we have assumed the optical eld is linearly polarized along the x-direction. Also, we have assumed that the optical wavelength is much greater than the size of the atom and therefore the spatial dependence of the optical eld is negligible (dipole approximation). Supposing the atom is originally at a certain eigen state |k, to obtain the linear response of the atom to the external eld, we calculate the wavefunction of the atom up to the rst order perturbation theory. In the interaction picture, V(t) = eiH0 t V(t)eiH0 t = |nm|dnm einm t E(t), (12.3)
n,m

where dnm en|x|m is the matrix element of the dipole and nm n m is the transition frequency, between the two states |m and |n. Up to the rst order perturbation, the wavefunction in the interaction picture is t t )dt |k = |k + i |(t) |k i V(t |ndnk eink t E(t )dt . (12.4)
n

To calculate the linear response, we just need to calculate the expectation value of the dipole moment d(t) = eiH0 t exeiH0 t = |nm|dnm einm t . (12.5)
n,m

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Using the wavefunction obtained from the rst-order perturbation theory, we have t (1) d (t) (t)|d(t)|(t) k|d(t)|k = +i dkn dnk eink (tt ) E(t )dt + c.c.
n k

(12.6)

This equation can be reformulated as d (t) =

(1) t

(1) (t t )E(t ),

(12.7)

with the linear susceptibility dened as [ ] (1) d(t ) k i k d(t )d(t) k i k d(t), d(t ) k . (t t ) +i k d(t)

(12.8)

The susceptibility has been written as the correlation of the position uctuation of the electron in the atom. The above correlation function is often written as a retarded Greens function [ ] r d(t ) k , G (t t ) i(t t ) k d(t), (12.9) so that the linear response is d (t) =
(1) +

Gr (t t )E(t ),

(12.10)

which has the physical meaning: The response is a linear combination of excitation created in the history and propagated to the time t. If the driving eld is oscillating with frequency , i.e., E(t) = E eit , ] [ dkn dnk dkn dnk (1) it d (t) = E e + G()E eit , (12.11) nk i nk + i + n k where an innitesimal positive decay rate is introduced to guarantee the causality. Thus, the polarizability spectrum is ] [ dkn dnk dkn dnk r it G() G (t)e dt = + . (12.12) nk i nk + i + n k To consider the case at nite temperature T , we just need to redene the Greens function (correlation of the uctuation) as averaged over the thermal distribution: [ ] ( [ ]) Gr (t t ) i(t t ) d(t), d(t ) = i(t t )Tr d(t), d(t ) . (12.13) The polarizability spectrum becomes G() = ek /(kB T ) [
k

n k

] dkn dnk dkn dnk + . nk i nk + i +

(12.14)

For a dilute atomic gas with density D and at a nite temperature T , the linear susceptibility is
1 () = 0 DG(),

(12.15)

12.2. FLUCTUATION-DISSIPATION THEOREM

173

where the normalization factor Z is the partition function. The polarization density at a given frequency is P() = 0 ()E(). (12.16) If the atomic gas has high density, the modication of the local eld due to the atom polarization need to be considered. The imaginary part of the polarizability spectrum, or the spectral density, is [ ] () = 2 G() ek /(kB T ) ek /(kB T ) = 2 |dnk |2 (nk ) 2 |dnk |2 (kn ) Z Z k n k k n k ( ) ek /(kB T ) (12.17) = 1 e kB T 2 |dnk |2 (nk ) , Z k n k with transparent physical meaning: The rst term corresponds to the dissipation due to transition to other states, and the second term corresponds to the gain due to transition from other states. The function gives the Fermi golden rule. Actually, the spectrum function is related to the absorption of the light. To show this, we note that the work done by an optical pulse to the atom is d W= dtF v = dtqE(t) = V dtE(t)P(t) = V r iE()P () 2 + + d d =V 2 [E ()P()] = V 20 [()]|E()|2 . (12.18) 2 2 0 0 The energy of the pulse is U=S 0 cE (t)dt = S
2 0

d 20 ()c()|E()|2 = S 2

d 20 ()c |E()|2 . 2 n()

The optical intensity is I = uc, I(L) = I(0)eL I(0) LI(0). The absorption coecient is () = [()]n() W() = . U()L ()c (12.19)

12.2 Fluctuation-dissipation theorem

Consider a general Hamiltonian H = H0 + HI
i

i Ni ,

(12.20)

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CHAPTER 12. LINEAR RESPONSE THEORY

where H0 is an non-interacting Hamiltonian which can be exactly diagonalized, HI contains the many-body interaction, and i is the chemical potential of the ith kind of particles. The density matrix of the system is 0 = 1 eH = 1 en |nn|, (12.21)
n

where H|n = n |n. We are to study the linear response of the system to a weak external force f (t), which drives the system through the interaction V(t) = A f (t), (12.22) where A = n,m Anm |nm| is a system operator. In the interaction picture, V(t) = eiHt V(t)eiHt = Anm |nm|einm t f (t) A(t) f (t). (12.23)
n,m

The Liouville equation in the interaction picture is [ ] t (t) = i V(t), (t) .

(12.24)

To study the linear response, we just need to derive the perturbation to the density matrix to the rst order of the external eld. The DM in the interaction picture is t [ ] (t) 0 + i A(t ), 0 f (t ). (12.25)

The change of the expectation value of a physical quantity B in the rst order of the perturbation is ( ) ( ) (12.26) B(t) Tr B(t)(t) Tr B(t)0 , where B(t) = eiHt BeiHt . With the density matrix solved, the linea response is t ( [ ]) Tr B(t) A(t ), 0 f (t ) B(t) =i ([ t ] ) =i Tr B(t), A(t ) 0 f (t ).

(12.27)

A retarded Greens function can be introduced as

([ ] ) Gr (t t ) i(t t )Tr B(t), A(t ) 0 .

(12.28)

The linear response thus can be expressed as + Gr (t t ) f (t ). B(t) =

(12.29)

Here we have use the condition that the system at thermal equilibrium has time-translational symmetry. By Fourier transformation B() = (12.30a) B(t) eit dt, () = f f (t)eit dt, (12.30b) () = Gr (t)eit dt, (12.30c)

12.2. FLUCTUATION-DISSIPATION THEOREM

the linear response in the frequency domain can be written as B() = () f(). Using the identity for the Heaviside step function + i 1 e () = , 2i i where is a positive innitesimal, the susceptibility can be written as S BA ( ) S AB ( ) d () = , i 2 with S BA ( S AB (
+

175

(12.31)

(12.32)

(12.33)

B(t)A(0) eit dt, A(t) B(0) eit dt.

(12.34a) (12.34b)

Here we have used the time-translational symmetry and A(0) B(t) = A(t) B(0) . The two functions dened above, called dynamic structure factors, have the physical meaning as the correlation function of the uctuations of the system at thermal equilibrium. The dynamic structure factors can be explicitly derived as en en S BA () = Bnm Amn eitimn t dt = Bnm Amn ( + n m ) , m m n n (12.35a) en en S AB () = Anm Bmn eitimn t dt = Anm Bmn ( + n m ) . m m n n (12.35b) The two factors are related by S AB () = e S BA (). (12.36)

In the special case that B = A , the factors are real and positive denite, with a transparent physical meaning: Transition rates governed by the Fermi golden rule. Eq. (12.36) depicts the principle of detailed balance: In thermal equilibrium, each transition is balanced (the incoming and outgoing scatterings are balanced). 1 Applying i = () to Eq. (12.33), we obtained the uctuation-dissipation theorem ( ) 1 e S A A () = 2(). (12.37) The imaginary part of the linear susceptibility corresponds to the absorption of energy from the external eld, or the dissipation. The physical meaning of the equation above is clear: The absorption of, e.g., a light, is due to transitions from lower energy states to higher energy states, minus the eect of gain due to transition from higher energy states to lower energy states (at equilibrium, the latter process has probability reduced by a factor of e ).

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12.2.1 Kramers-Kronig relations

The real and imaginary parts (in linear optics, one corresponds to refractive index, and the other corresponds to absorption) are related by the K-K relations. We notice that the linear susceptibility is the Fourier transform of the retarded Greens function, which is zero for t < t . This means the susceptibility () has no singularity point in the half complex plane above the real axis. The susceptibility of a realistic physical system should vanish as . Thus we have the following relation + () d = 0. (12.38) + i Using we have P Thus we have the K-K relations as () = P () = +P 1 1 =P i( ), + i
+

(12.39)

() d = i().
+

(12.40)

() d , () d .

(12.41a) (12.41b)

12.3 Density uctuation and structure factor

In X-ray scattering, neutron scattering, etc., the linear responses give the structure information of the (spin) density uctuations in the system (such as in the case of emergence of antiferromagnetism). In this Section, we formulate the linear response theory for such measurement. We consider the coupling of an external eld f (x, t) to the density n(x) through the Hamiltonian V = n(x) f (x, t)dx. (12.42) The linear response can be written as n(x, t) = where the Greens function [ ] Gr (x, t; x , t ) = i(t t ) n(x, t), n(x , t ) . In quantum mechanics, the density operator can be written as 1 1 iqx n(x) = (x)(x) = Ckq, ck, e (q)eiqx , V k,q, V q (12.44) Gr (x, t; x , t ) f (x , t )dx dt , (12.43)

(12.45)

12.4. KUBO FORMULA

177

where k and q are momenta, is spin, and (q) is the density operator in the momentum space. Fourier transformation of the linear response gives (q, ) = (q, ) f(q, ), with (q, ) = f(q, ) = (q, t)eit dt, (12.47a) (12.47b) (12.47c) (12.46)

f (x, t)eitiqx dxdt, [ ] i (q, ) = ei () (q, ), (q, 0) d. V

The dynamic structure factor is dened as 2 S (q, ) ei (q, )(q, 0) d = 2 1 en n|rho(q, 0)|n ( + n m ).
n,m

(12.48) Here we have used the translational symmetry of the system. Corresponding to the general case that B = A , (since (q) = (q)), the dynamic structure factor is real and positive denite. The susceptibility for an external eld with a certain wavevector (q) and frequency () is related to the structure factor 1 S (q, ) S (q, ) d (q, ) = . (12.49) V i 2 The response to a static and uniform external eld corresponds to the case that q = 0 and = 0. The uctuation-dissipation theorem takes the form ) 1( 1 e S (q, ) = 2(q, ). V (12.50)

12.4 Kubo formula

In transport experiments, the conductivity of a system is measured, which is dened by j = E , (12.51)

where E is the electric eld along the -direction, and j is the current density along the direction. The current density operator is = j(x) q m (rm x), r (12.52)
m

where q is the charge, and rm is the position of the mth particle. The interaction Hamiltonian under an external eld is V = q rm E(t). (12.53)
m

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CHAPTER 12. LINEAR RESPONSE THEORY

Here we assume the electric eld is uniform. The linear response theory give the current density as ] iq2 t [ rm (t), rn, (t ) E (t )dt . j = V n,m,

(12.54)

Using the time-translational symmetry of the system and the cyclic permutation symmetry of operators under trace operation, we rewrite the formula above as t [ ] j (t) = i Tr j (t t ) q rn, , E (t )dt , (12.55)
n,

where = 1 exp(H) is the density matrix of the system. For an arbitrary operator A, the commutator with the density matrix can be written as ( ) ( ) [ ] A, = 1 AeH eH A = eH AeH A . (12.56) Using d H H e Ae = eH [H, A] ebetaH , d we have [ A, =
0

(12.57)

e [H, A]e

d = i
0

eH AeH d.

(12.58)

The integrand has the form of an operator in the interaction picture at an imaginary time i, dened as A(i) eH AeH . (12.59) Thus we have [ ] rn, , = iV q
n 0

(i)d. j

(12.60)

The linear-response current density becomes j (t) = V d d (i) () E (t ). j j

0 0

(12.61)

In particular, for a static external eld j = V d d (i) () E . j j

0 0

(12.62)

and the conductivity is given by the Kubo formula = V d d (i) () , j j

0 0

(12.63)

which has the form of current-current correlation function. At the high temperature limit, 0, j(i) for [0, ], so j(0) = V j j (12.64) d (0) () .
0

This is another example of the uctuation-dissipation theorem.

12.5. ONSAGER RELATIONS

179

12.5 Onsager relations

12.5.1 Generalized forces and current
Above we considered the electric force and current. In general, when a system is brought away from the equilibrium state, generalized forces and hence currents may be generated. The electric eld corresponds to an electrostatic potential over the space. At equilibrium, a thermodynamic system should have uniform temperature, chemical potential, pressure, etc. When there are gradients of such variables, the system is out of equilibrium, and currents will be generated to recover the equilibrium. Similar to the electric eld, we can relate the gradients to the generalized forces, such as chemical potential gradients, temperature gradients, etc. We consider the case that the system is only slightly away from the equilibrium state, and the current is linear to the gradient. The current will generate entropy in the system, as a spontaneous process. In equilibrium, we have the energy conservation condition ds = 1 1 1 de Xi di j dn j k dk , T T i T j k (12.65)

where s is the entropy density, e is the energy density, Xi is pressure, magnetic eld, etc, and i the corresponding densities. When the potential k has spatial variation, the system is out of equilibrium, and the generalized force will drives a current. The ow of the density k creates a current jk , which satises the conservation condition t k + jk = 0. (12.66) In the linear response regime, the currents are related to the forces k through a set of coecients (called kinetic coecients), jk = Lkl l + O (k )2 . (12.67)
l

Note that, there may be o-diagonal terms, which means, e.g., a temperature gradient may cause an electric current (Seebeck eect).

12.5.2 Entropy generation

The currents will generate an entropy current as js = k jk .
k

(12.68)

The total charge of entropy is given by both the variation of the densities and the currents, i.e., d s = t s + j s , dt where t s =
k

(12.69)

k t k .

(12.70)

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CHAPTER 12. LINEAR RESPONSE THEORY

Finally, we get the entropy generation rate as d s= jk k . dt k

(12.71)

12.5.3 Onsager relations

As a result of the microscopic reversibility, the kinetic coecients are related by the Onsager relations Li j = L ji . (12.72) Someone call this relation the fourth law of thermodynamics. To show such relations, let us express the thermodynamic variables k by a set of microscopic variables 1 , 2 , . . . , N , which are zero at equilibrium with maximum entropy. The probability distribution of these variables is P() = eS (1 ,2 ,...,N )/kB deS (1 ,2 ,...,N )/kB . (12.73)

Since the entropy has maximum value when = 0, we have 1 P() = C exp k1 n gnm m , 2 B n,m

(12.74)

which is a Gaussian function, with g being a positive denite matrix and C a normalization factor. A useful expression for the correlation function is S S P() n = dn P() = kB dn = kB n,k . (12.75) k k k This means at thermal equilibrium, the uctuations are isotropic (recall that the energy partition law). To consider the linear response, we dene a generalized force Xn due to deviation of the variable n from the equilibrium value. The current is jn = d n . dt S . n (12.76)

Using Eq. (12.71), the corresponding generalized force can be written as Xn = The linear response can be written as jn = or
m

(12.77)

Lnm Xm ,

(12.78)

d S n = Lnm . dt m m

(12.79)

12.5. ONSAGER RELATIONS

181

The susceptibility is related to the correlation function. The expectation value of two variables at dierent time can be written as n (t + t)m (t) = n (t + t)m (t) + tn (t)m (t) S Lnk = n (t)m (t) + t m k k = n (t)m (t) tLnm kB . Here Eq. (12.75) has been used. Similarly, m (t + t)n (t) = m (t)n (t) tLmn kB . (12.81) (12.80)

The microscopic reversibility principle states that if the uctuation of one microscopic variable causes the uctuation of another variable at an innitesimal later time, the uctuation of the latter variable will also cause the uctuation of the former variable at an innitesimal later time, with the same amplitudes. Thus, n (t + t)m (t) = m (t + t)n (t). (12.82)

With this reversibility condition, the Onsager relations follows. If the system is under a magnetic eld B, which changes the sign under time-reversal transform, the Onsager relations should be modied to be Li j (B) = L ji (B) . (12.83) The Onsager relations reect the profound relations between linear responses and the correlations of uctuations. When a system is at thermal equilibrium, the uctuations can go both directions. Over an innitesimal time, the uctuations must have the microscopic reversibility. The o-diagonal kinetic coecients induced by cross correlations between dierent uctuations must be symmetric under exchanges of subscripts.

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Bibliography
[1] M. Plischke and B. Bergersen, Equlibrium Statistical Physics, 2nd ed. (World Scientic, Singapore, 1994), Ch. 10. [2] G. D. Mahan, ManyParticle Physics, 3rd ed. (Springer, Berlin, 2010). [3] R. Kubo, J. Phys. Soc. Japn 12, 570 (1957). [4] L. Onsager, Phys. Rev. 37, 405 (1931). Reciprocal Relations in Irreversible Processes.

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