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Physics 212: Statistical mechanics II, Fall 2006 Lecture VIII

Now we turn to a quantum-mechanical version of the physics of the previous lecture. Let us begin with a short review of some facts from quantum statistical mechanics: the Hamiltonian of a system determines both its energy levels (its statics) and its time evolution (its dynamics). The time evolution of a state in the Schrodinger picture is given by i h or for a time-independent Hamiltonian
h (t) = eiHt/ (0).

= H, t



The time evolution of the expectation value of an operator can be determined from the above:
h h O (t) = (t)|O|(t) = (0)|eiHt/ OeiHt/ |(0) ,


so it is also valid to use the Heisenberg picture where states are constant but operators evolve as h h O(t) eiHt/ O(0)eiHt/ . The fundamental object of quantum statistical mechanics is the density matrix . Recall that classical stat. mech. averages can be written O = The quantum-mechanical version of this is T r eH O = O = T r O = T r eH

H i Oi e . H ie


eE |O



where the trace is taken over a full set of states (assumed to be energy eigenstates in the second equality) and the density matrix at equilibrium is eH . T r eH (6)

This density matrix is normalized to 1 and satises the other properties of a density matrix mentioned in quantum mechanics textbooks (some of these properties are reviewed in a moment). Below we will consider other density matrices representing changes in the above equilibrium distribution. The quantum denition reduces to the classical one in the event that all observables commute, as it should. We will see below that uctuation-dissipation ideas are if anything even simpler in the quantum case. Now we give a brief review of density matrices, as we will have to consider perturbations to the equilibrium density matrix dened above. Consider a quantum-mechanical system of states |n . The expectation value of an operator A in the pure state |i is just i|A|i . Suppose that there is a 1

large ensemble of systems, each of which is in one pure state. If the probability of a system being in state i is Wi , then we have the overall normalization Wi = 1


and the statistical average value of an operator A over the ensemble is A =


Wi i|A|i .


Now the above formula makes no assumption about the orthogonality of the states |i . The density operator is explicitly written as


| W |,


where | are some normalized states (not necessarily orthogonal or complete). This is now shown to reproduce the sort of statistical average discussed above. Lets take an operator A and ask about its statistical expectation. In a particular orthonormal basis, the matrix representation of is

n,n = n||n =

n| |n Wi .


Now T r A =

n,n An ,n =
n,n ,

n| |n W n |A|n .


We can simplify this greatly using the completeness relation for the basis |n : completeness requires |n n| = 1.


Then in the above sum, both the sums over n and n just give unity, leaving T r A =

W |A| .


Some simple properties of the density matrix that follow from the above denition are Tr = 1 (14)

and all diagonal elements are nonnegative, since the diagonal elements are just the probabilities of being in dierent pure states. Can you show that for a pure state, 2 = ? Finally, the evolution of the density matrix under the Hamiltonian H is h d = i[H, ] = i(H H). dt (15)

To understand this, recall that the basis-invariant denition of is



| W |. 2


Then, in the Schrodinger picture where time dependence is carried by the states, the time derivative is d dt


d| d | W | + | W dt dt | W | +
i i

iH h

| W |

iH . h


Then we obtain the above equation. Henceforth in this lecture we set h = 1. A standard method of quantum mechanics is to divide a Hamiltonian into two parts, a starting part H0 and a small perturbation H1 . A small perturbation H1 added to the equilibrium distribution at some time is expected to introduce a small change in the values of statistical averages at all later times, which we now attempt to calculate. Write H = H0 + O1 (t), (18) so H1 (t) = O1 (t). The evolution of the density matrix in the Hamiltonian H (see above) is h d = i[H, ] = i(H H). dt (19)

h h For a time-independent Hamiltonian, this is satised by (t) = eiHt/ (0)eiHt/ . You can show that the equilibrium density matrix is constant in time by noting that both it and H are diagonal in a basis of energy eigenstates.

We want to consider the case of a system whose density matrix begins in the equilibrium distribution eq of H0 at time t0 . This density matrix evolves with time once the perturbation is turned on. Dene the so-called Liouville operators L0 and L1 through iL0 = i[H0 , ]/ , h Then iL1 = i[O1 , ]/ . h (20)

d(t) = iL0 + iL1 (t). (21) dt We want to turn the dierential equation for the evolution of into an integral equation. Consider

(t) = exp(i(t t0 )L0 )(t0 ) +


dt exp(i(t t )L0 )iL1 (t )(t ).


Taking the derivative of this equation should turn out to give the time evolution equation (21). The rst term gives iL0 exp(i(t t0 )L0 )(t0 ). The second term gives two parts: iL1 (t)(t), from the upper limit of integration, and

dt iL0 exp(i(t t )L0 )iL1 (t )(t ).



This second part, combined with the rst term, is just iL0 (t). Hence the time evolution equation is indeed satised. Note that this integral equation is very similar to that for u(t) in the classical case (??) above. 3

The point of this rewriting is that the integral equation can be linearized for small ; the approximation involved is that (t ) in the integrand is now replaced by eq . Doing so and taking t0 = gives i t h h dt ei(tt )H0 / [H1 (t ), eq ]ei(tt )H0 / . (24) (t) = eq h This equation gives the change induced in the density matrix by the perturbation H1 . Finally, let us ask how the value of an observable O2 at time t is modied. The change in the 2 is value of O O2 = T r (t)O2 T r eq O2 t i h h = dt T r ei(tt )H0 / [H1 (t ), eq ]ei(tt )H0 / O2 . h


Now we will complete the derivation of the quantum version of linear response. Return to the above integral equation for the density matrix time evolution,

(t) = exp(i(t t0 )L0 )(t0 ) +


dt exp(i(t t )L0 )iL1 (t )(t ).


In the limit of small , the (t ) can be replaced by eq inside the integral, as L1 is already of order so anything resulting from the dierence in this replacement will be of order 2 . Remember that the action of L1 was dened to be iL1 = i [O1 , ], h (27)

so that iL0 + iL1 gives the full time evolution under H. Finally note that the density matrix eq is invariant under H0 , and take t0 . With these substitutions, the above integral equation becomes t i dt exp(i(t t )L0 )( (t) = eq + [O1 , eq ]). (28) h Finally, substituting in the action of L0 , using its time-independence, and setting = 1 gives h

(t) = eq +

dt exp(i(t t )H0 )(i[O1 , eq ]) exp(i(t t )H0 ).


Our goal is to understand how the value of an observable O2 at time t is modied. The change in the value of O2 is O2 = T r (t)O2 T r eq O2

= i

dt T r ei(tt )H0 [O1 (t ), eq ]ei(tt )H0 O2 dt T r [O1 (t ), eq ]O2 (t t ) . (30)

= i

Here we have used the cyclic property of the trace in the last line, and O2 (t t ) indicates the 2 , Heisenberg-evolved O O2 (t t ) ei(tt )H0 O2 ei(tt )H0 . (31) 4

One last simplication that can be made by cycling factors in the trace gives O2 = i

dt T r eq [O2 (t t ), O1 (t )] .


Since the trace of a quantity with respect to the equilibrium density matrix is just the statistical expectation, this can be written as O2 = i

dt [O2 (t t ), O1 (t )] .


This is the fundamental quantum statement of linear response. It can be used to derive quantum equivalents of the conductivity formula given previously. Occasionally it is written in the simplied notation t O2 = dt O2 (t t ), O1 (t ) , (34) h where (A, B) i[A, B], so that (A, B) is Hermitian if both A and B are Hermitian, and we have restored the factor of h. Note that all the quantum systems we study have a Hamiltonian and hence a uniquely specied dynamics. In some classical systems such as the Ising model, one has an energy functional but no associated Hamiltonian, so one is free to choose the dynamics using physical principles such as detailed balance. In the Langevin equation for Brownian motion, we similarly used the physical requirement of thermal equilibrium to constrain a model for the dynamics. Parenthetical note I: Classically we considered Brownian particles with charge e and have density n: then the Langevin equation predicts that the average current in an electric eld E is j(t) = ne u(t) = Re((0 )K0 ne2 ei0 t ), where the complex mobility is () =


eit u(0)u(t) .


The quantum-mechanical version of this is known as the Kubo formula (this term is also sometimes used for the general linear-response formula derived above): the conductivity is given by the correlation function of the current at time 0 with the current at time t. Parenthetical note II: You might ask, given the density matrix, how to express the entropy of a quantum system. The logical denition is the von Neumann entropy, dened as S() = T r log2 . (37)

For a diagonal density matrix with equal probabilities (this is a mixed state) this reduces to the classical entropy up to a constant. Any pure quantum mechanical state has entropy 0, since a pure state can be converted by a change of basis to a matrix with diagonal elements 1, 0, . . . , 0. This is connected to some recent developments in the theory of entanglement of quantum systems. Suppose that a quantum system is divided into two subsystems A and B, and that the whole system is in a pure state = | |. (38) 5

We can dene the reduced density matrix for subsystem A by a partial trace over subsystem B: 1 |A |2 =

( 1 | j |)| |(|2 |j ).


Note that this can be a mixed density matrix even if we started from a pure state for the whole system. As an example, consider the state (| | )/ 2 for a state of two spin-half. You can conrm by a simple calculation that this gives 0 for a product state | = | 1 | 2 , and 1 for a fully entangled state of two qubits (e.g., a singlet (| | )/ 2.