Handout on Kramers-Kronig relations Refer to Chapter 11 of Kittel. The purpose here is to prove the Kramers-Kronig relations.

Further, we show an application of using the K-K relation in an application of analyzing the reectance spectrum. The result that we would like to get is, e.g., 1 () 1 = and, 2 2 () = P
0

2 P

2 ( ) , 2 2

(1)

1 ( ) , 2 2

(2)

where P is the principal value. (This application has to do with the fact that = 1 + 4, that is, is actually the response function of interest.) The usefulness is that if either 1 or 2 is known (experimentally measured), the other can be calculated. We observe from the functional form and learn quickly that only for near would the contribution from 2 be important to construct 1 , and vice versa. In practice, this (limited frequency range in integration) is helpful, since its impractical to measure the entire spectrum from DC for X-ray. There are several components in the proof. What we will do is to chop the proof in several components, and then use the derived results one by one. First, the linear response theory. Linear response function and susceptibility An external inuence f produces a response y of the system. For example, an external electric eld can induce the dipole moment of a gas atom. We assume here that the response is linear, and y(t) depends only on what happened before y is measured at time t. So, we rst assume that (A) the sample system is linear in response and (B) the causality. Thus, we dene:

y(t) =

dt K(t t )f (t ),

(3)

where the function K is the response function, and f is the force (or called stimulation). Note that instead of a general response function, K(t, t ), we use K(t t ) to show that the system is invariant under a translation in time. Dene = t t , we have

y(t) =

d K( )f (t ). 1

(4)

Note here that we integrate from zero. This is because by denition, is larger than zero. That is, what happens at time t can be aected only by input that occurs earlier. We further assume that: (A) K is real, thus when f is real, y is real; and (B) K = 0 for < 0, thus,

y(t) =

d K( )f (t ).

(5)

Note that with the denition of K, the integration starts from negative innity again. The nature of K can be learned by this: letting f (t ) = (t ), so

y(t) =

d K( )f (t ) = K(t).

(6)

That is, the physical meaning of K is that it is the response of the system under a -function excitation. Working in the Fourier-transformed space is often more convenient The Fourier transform of f is:

f (t) =

df ()eit,

(7)

and, f () = 1 2

dtf (t)eit .

(8)

Now, plug the FT form (of f (t)) into equation (6), we get:

y(t) =

d K( )

df ()ei(t ) =

d()f ()eit,

(9)

where

() =

d K( )ei .

(10)

So, by observing this functional form, we learn that the function (), the susceptibility, is therefore the Fourier Transform of K(t). Symmetry property of the susceptibility 2

We learned from equation (9) that y() = ()f (). Since K( ) is real, we have: (()) = (). So, when considering the real and the complex parts of , we have: = + i , and () = (); () = (). That is, () is even and () is odd. Complex Normally, is real when doing experiments. But, its often more convenient to provide additional exibility by using a complex (for mathmatical arguments):

(11)

(12)

(13)

() =

d K( )ei .

(14)

Let = r + i i , then
d K( )ei = d K( )ei r i .

( ) =

(15)

And, since K( ) is real,

d K( )ei r i =

( ) =

d K( )ei( r +i i ) = ( ).

(16)

Because of causality, we observe (from equation (14)) that ( ) = 0 if < 0, since K( < 0) = 0. But, if > 0, i must be > 0, for otherwise ( ) will diverge (see equation (15)) and become unphysical. From this observation, we acknowledge that i > 0, i.e., i rests on the upper half of the complex plane. The nature of the property of () makes i positive. So, our conclusion is that > 0 and i > 0. K-K relations Whats interesting is that and are not two independent variables. They are related by the K-K relations. In the following we use results from the above pieces and derive the K-K relations. 3

First, if the () = () + i () has no singularities within the contour, then d ( ) =0= + + + .

(4)

(1)

(2)

(3)

(17)

The contour for the Cauchy principal value integral and the denition of the four segments are denedx in Kittel (see drawing in Fig. 2, chapter 11, page 311, 7th edition) and repeated here:
(1)

=
R

, is the half circle above = , integrated clockwise,

(18)

(2)

R (3)

=
+

, = is the half circle above = , integrated counter-clockwise.

(19)

and

(4)

1 We further take a physical assumption that |( )| goes to zero faster than | | as goes to . Given this assumption, we have for the 4th term:

R,0 C

lim

( ) = 0.

(20)

The integration of half circle C can be treated by assuming that = + ei , and, thus, d = iei d, = ei . The 2nd term is therefore obtained to be: lim ( ) d = lim R,0 C
0

(21)

(22)

R,0

( + ei ) i d ie = i(). ei

(23)

The principal value is the sum of the 1st and the 3rd term: T erm1 + term3 = 0 term2 term4 = i =

( ) = lim R,0

+
R

R +

= i() = i(( ) + i( )). 4

(24)

Now, separate equation (24) into the real and imaginary parts, we reach the important conclusion: () = and 1 () = P

1 P

( ) ,

(25)

( ) .

(26)

We would like to integrate over only the positve by using the facts that () is even and () is odd. So, by multiplying the expressions in (25) and (26) by + , + and use the property that

(27)

(oddf unction) = 0,

(28)

we get (from equation (25)): () = 1 P

( )( + ) 2 = P 2 2

( ) , 2 2
oddodd even

(29) =
even even

(in the last equation the integrand has this symmetry () = 1 P

= even) and (30)

2 ( )( + ) = P 2 2
even even

( ) . 2 2

(the last integrand has symmetry

= even.)

Equation (29) and (30) are one form of the K-K relations, in the sense that the K-K relation has been widely applied. We can identify a physical quantity Q = Qreal + iQimaginary (a response function of a system) with . For example: [ () 1] () n() 1 () . Application in reectance spectrum.

(31)

The reection coecient can be represented by its amplitude and phase: r() = Eref lection n + i 1 = ()ei() = . Eincident n + i + 1 (32)

n is called the index of refraction, and is the extinction coecient. The reectance R = |r|2 = 2 . Now, 1 ln r() = ln R() + i(). 2 We then identify: () . So, applying the K-K relations, 2 P
0 1 ln R( ) 1 = d 2 2 2 2 0 1 ln R() 2

(33)

(34)

() =

d ln |

+ d(ln R( )) | d , d

(35)

as shown in Kittel. So, when R is experimentally measured, can be calculated. Once R and are known, the reection coecient r is calculated, and serveral the other macroscopic optical constants can be subsequently calculated: n() = 1+r21r , 2rcos() 2rsin() () = 1+r2 2rcos() , 1 () = n2 2 , 2 () = 2n.
2

(36)