Kubo Formula for Electrical Conductivity

Linear response to external perturbation: Out signal intensity of external perturbation.

Kubo formulas: correlation functions describing the linear response.

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Electrical conductivity:

Response of solid (i.e., induced current) to external electric eld. External electric eld: E (ext)(r; t) = (ext) ei(q r !t); Linear response ) Induced current: J (r; t) =
P

= x; y; or z:
0 (q; !) E (ext)(r; t):

The desired conductivity, , is, however, the response to the total internal P el. eld in the solid, E (r; t) = (external and induced elds). De nition of :

J (r; t) =

(q; !) E (r; t) )

(1) (2) (3)

2

E (r; t) = ei(q r !t) = Re( ) + i Im(

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2. A single freq. ! perturbs the system and (q; !) is the response to this !. However, we assume a linear system and that perturbations at di erent P !'s act separately ) total current = over each !.

1. Long-wavelength excitations are studied (small q): Def. (1){(3) correct only for homogeneous material ( is a function of distance from el. eld) ) Incorrect on atomic scale. However, valid if J is to be averaged over many unit cells (e.g., q is small). Often we are interested in the dc conductivity ) q ! 0 and ! ! 0.

Assumptions:

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^ ^ Hamiltonian: H + H 0 ^ H : Hamiltonian without electric eld

(contains however all other interaction terms).

^ H 0: Interaction between el. eld and particles: 1 hp ei A(r ; t)i2 ^ H 0 = 2m i c i i

X X

1 p2; 2m i i
, \transverse" eld).

(4)

if we choose the potentials r

A = 0 and ' = 0 (

i.e.

r A = 0 is the Coulomb gauge , Instantaneous Coulomb interaction.

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Maxwell & de nition of A )

E
1A c

= =

1 @A ) c @t iE = i ! !

(5)

ei(q r !t)

(6)

Linear response ) drop (A)2 terms )

^ 0 = e 1 X pi H c 2m i

A(ri; t) + A(ri; t) pi]

(7)

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Probability current density j0:

@ j j2 @t i ) j0(r; t) = 2m (r; t) r (r; t) (r; t) r (r; t)] ) De ne current operator: 1 X e (r r )p + p (r r )] ^(r) = j i i i i 2m i i

r j0(r; t) =

(8) (9)

(10)

) Perturbation Hamiltonian:

^ H 0 = 1 d3r ^(r) A(r; t) j c

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(11)
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Fourier transform ^(r): j

1 X e eiq r p + p eiq r ^(q) = j i i 2m i i

i

(12)

^ We can then get rid of d3r in H 0:

R

^0 = i H !

e i!t ^(q) j

(13)

Observable current J(r; t) = average of particle velocities:

e Xhv i; ^ J(r; t) =
i i

(14)

where is the volume.

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But:

r ^ vi = ddti =

^ ^ ri ; H + H 0

1 hp e A(r )i = m ^i c i
X

(15) (16) (17) (18)

e Xhp i e2 ^ i mc ) J(r; t) = m i
Also:

A(ri; t)

^i = e pi ; 1 A(r; t) = i E(r; t) j m^ c !

where
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= n0 = particle density, if long-wavelength perturbation.

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e2 n E(r; t); ) J(r; t) = h ^(r; t)i + i m! 0 j

Thus: where:

J = J(1) + J(2); J(1)

in0e2 E(r; t); = m! = h ^(r; t)i: j

(19) (20) (21)

J(2)

What is the constant of proportionality between J(2) and E, assuming linear response? ! Kubo formula!

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In Heisenberg representation:

Transverse Fields, T = 0
0 0

^ ^ ^ ^ j j J (2)(r; t) = h ^ (r; t)i = h 0jei(H +H )t ^ (r) e i(H +H )tj 0iH

(22)

^ In Interaction representation, with H 0 as perturbation:

^ ^ ^ iHt e i(H +H )t (0) (t) = e
0

^ U (t) (0)
^ ^ iHt U (t)j 0iI

(23) (24)

^ ^ ) J (2)(r; t) = h 0jU y(t) eiHt ^ (r) e j

^ ^ j 0i: wavefn. at t = 0 with H + H 0. ^ ^ As before: U (t) j 0i = S (t; 1) j i, where j i: wavefn. with H 0 = 0.

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Then:

J (2)(r; t) = h jS y(t; 1) ^ (ri; t) S (t; 1)j iI; h j Rt ^ where: S (t; 1) T exp i 1 dt0 H 0(t0) .
^ Linear response ) keep only terms linear in H 0:
Z

(25)

S (t; 1) = 1 i

1
Z

^ ^ dt0 H 0(t0) + O(H 02):

(26)
i

) J (2)(r; t) = h

j^ (r; t)j i i j

dt0h

^ ^ (r; t); H 0(t0) j

j i:

(27)

h j^ (r; t)j i = 0, since no current if no eld. j

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^ i H0 = !
h

^ (q) e i!t ) j
i

^ ^ (r; t); H 0(t0) j

i e i!t h^ (r; t); ^ (q; t0)i = j j = ! i E (r; t) e iq r ei!(t t ) h^ (r; t); ^ (q; t0)i ; (28) = ! j j
0 0

which shows that J (2) is proportional to the el. eld. The constant of proportionality thus is:

1 e iq r Z t dt0 ei!(t t ) h j h^ (r; t); ^ (q; t0)i j i + n0e2 i (q; !) = ! j j m! 1

0

(29)
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Remains: Average over r to get rid of atomic uctuations (i.e., integrate d3r and divide by ). Only r dependence:
R Z

d3r e iq r j (r; t) = j ( q; t) = j y (q; t);

Z

(30)

giving the Kubo formula:

1 1 dt ei!t h j h^y (q; t); ^ (q; 0)i j i + n0e2 i (q; !) = ! j j m! 0

where we have changed the integration variable: t t0 ! t.

; (31)

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The Kubo formula contains a retarded, two-particle Green's function. De ne the retarded correlation function of the current operator:

i (t t0) h j h^y (q; t); ^ (q; t0)i j i (q; t t0) = j j

with Fourier transform (the \current-current correlation fn."):

(32)

i Z 1 dt (t t0) ei!(t t ) h j h^y (q; t); ^ (q; t0)i j i; (33) (q ; ! ) = j j

0

yielding:

i (q ; ! ) = !

n0e2 (q; !) + m

(34)

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Easiest in practice: Evaluate the Matsubara current-current correlation fn.:

(q; ) = (q; i!) =

Z

1 hT j y (q; ) j (q; 0)i

0

(35) (36)

d ei!

(q; );

and then obtain the retarded fn. by changing i! ! ! + i .

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Take rst limit q ! 0 and then ! ! 0. to seek new equilibrium.

dc Conductivity

Order is important: ! = 0, q 6= 0 ) static eld, and charge will be allowed

q ! 0: No problem, since ^(q) is well behaved. j

! ! 0: Problem with 1=! factor.

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dc conductivity: real, Re

1 ] = lim!!0 ! Im

(!)].

Introduce spectral function of Im

(!), R (!) (cf. Eq. (3.3.13) in Mahan):

1 R (!) = (!)] = 2 = (1 e ! ) e+ X e E hnj^y jmi hmj^ jni (! + En Em) (37) j j

n

n;m

The ! prefactor is thus:

1 lim0 ! (1 e ! ) = !!

(38)

It is also possible to derive the ! = 0 result directly: See Section C!

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and answer as above!

Longitudinal Field, Finite Temperatures Longitudinal eld: Allow for a non-zero longitudinal A ) same derivation

^ Finite temperatures: Should H 0 go directly into the thermodynamic weighting ^ ^ ^ factor exp ( H H 0 + N )]?
Answer: No! If the time oscillation of the eld is fast enough, the heat bath will not follow it! Also: such an ansatz would yield that the time dependence of the current operator plays no role, which is non-intuitive.

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Write: J (2) = h^ (r; t)i = Tr ^(t) j ], j i.e., hide all time operators into a time-dependent density operator ^(t).

^ Let H 0(t = 1) = 0 ) ^0 = ^(0) = exp (

^ ^ H + N )].

^ Switch then on H 0 adiabatically until the present time. ^(t) obeys a Heisenberg equation of motion: d ^(t) = i hH + H 0(t); ^(t)i ^ ^ dt ^ Let ^(t) = ^0 + f (t) )
(39)

d f^(t) = hH; ^ i + hH; f^i + hH 0; ^ i + hH 0; f^i ^ 0 ^ ^ 0 ^ i dt

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(40)
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^ ^ ^ ^ Use H; ^0 = 0, keep only terms linear in H 0 (and use f H 0) )

d f^(t) = hH; f^i + hH 0; ^ i : ^ ^ 0 i dt

Rearrange:

(41)

d f^(t) hH; f^i = hH 0; ^ i ^ ^ 0 i dt d eiHt f^(t) e iHt eiHt = hH 0; ^ i ^ ^ ^ ^ 0 e iHt i dt ^ d eiHt f^(t) e iHt = eiHt hH 0; ^ i e iHt = hH 0(t); ^ i ^ ^ ^ ^ ^ i dt ^ 0 0
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Integrate:

f^(t) = f^( 1) i e

^ iHt

^ dt0 H 0(t); ^0

^ eiHt; f^( 1) = 0 (42)

^ j j Now: J (2)(r; t) = Tr ^(t) ^ (r)] = Tr ^0 ^ (r)] + Tr f (t) ^ (r)] j

Tr ^0 ^ (r)] = 0, since no current if no eld. j Thus:

J (2)(r; t) =
=
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i Tr e i Tr
Z

1 t i h ^ ^ 0 H 0(t0); ^0 eiHt ^ (r) e iHt = dt ^ j 1

^ iHt

^ ^ dt0 H 0(t0); ^0 eiHt ^ (r) = j

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= = =

i Tr i Tr i
Z

Z Z

t t

^ dt0 H 0(t0); ^0 ^ (r; t) = j ^ dt0 ^0 ^ (r; t); H 0(t0) j

h i

1 t h i 0 h ^ (r; t); H 0(t0) i; ^ dt j 1

=
(43)

which is the same expression as Eq. (27) before. We thus get the same Kubo formula as in the T = 0 case. However, there: h i = expectation value in ground state at T = 0, while here: h i = thermal average.

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