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The problem of quantum statistical mechanics is the quantum mechanical treatment of an N -particle system. Suppose the corresponding N -particle classical system has Cartesian coordinates

q1 ; :::; q3N

and momenta

p1 ; :::; p3N

and Hamiltonian

H=

3N X

Then, as we have seen, the quantum mechanical problem consists of determining the state vector j (t)i from the Schrodinger equation Denoting the corresponding operators, Q1 ; :::; Q3N and P1 ; :::; P3N , we note that these operators satisfy the commutation relations:

@ H j (t)i = ih @t j (t)i

Qi ; Q j ] = P i ; P j ] = 0 Qi ; Pj ] = ihI ij and the many-particle coordinate eigenstate jq1 :::q3N i is a tensor product of the individual eigenstate jq1 i; :::; jq3N i: jq1 :::q3N i = jq1 i jq3N i The Schrodinger equation can be cast as a partial di erential equation by multiplying both sides by hq1 :::q3N j: @ hq1 :::q3N jH j (t)i = ih @t hq1 :::q3N j (t)i # " 3N X h2 @ 2 @ ? 2m @q2 + U (q1 ; :::; q3N ) (q1 ; :::; q3N ; t) = ih @t (q1 ; :::; q3N ; t) i i i=1

where the many-particle wave function is (q1 ; ::::; q3N ; t) = hq1 :::q3N j (t)i. Similarly, the expectation value of an operator A = A(Q1 ; :::; Q3N ; P1 ; :::; P3N ) is given by

@ hAi = dq1 dq3N (q1 ; :::; q3N )A q1 ; :::; q3N ; h @q ; :::; h @q@ i i

1

3N

In general, the many-body wave function (q1 ; :::; q3N ; t) is far too large to calculate for a macroscopic system. If we wish to represent it on a grid with just 10 points along each coordinate direction, then for N = 1023, we would need 23 1010 total points, which is clearly enormous. We wish, therefore, to use the concept of ensembles in order to express expectation values of observables hAi without requiring direct computation of the wavefunction. Let us, therefore, introduce an ensemble of systems, with a total of Z members, and each having a state vector j ( )i, = 1; :::; Z . Furthermore, introduce an orthonormal set of vectors j k i (h k j j i = ij ) and expand the state vector for each member of the ensemble in this orthonormal set:

( )

i=

( Ck ) j k i

The expectation value of an observable, averaged over the ensemble of systems is given by the average of the expectation value of the observable computed with respect to each member of the ensemble: 1 hAi = Z Substituting in the expansion for j

( )

Z X

=1

( )

jAj

( )

1 hAi = Z =

i, we obtain

X

k;l

( Ck ) Cl( ) h k jAj l i

k;l

Z 1 X C ( )C ( l k Z

=1

!

)

h k jAj l i

Let us de ne a matrix

lk =

Z X

=1

( Cl( ) Ck

Z 1X ( ~lk = Z Cl( ) Ck

=1

Thus, lk is a sum over the ensemble members of a product of expansion coe cients, while ~lk is an average over the ensemble of this product. Also, let Akl = h k jAj l i. Then, the expectation value can be written as follows: X X A = 1 ( A) = 1 Tr( A) = Tr(~A) hAi = 1

Z k;l lk kl

Z k

kk

where and A represent the matrices with elements lk and Akl in the basis of vectors fj k ig. The matrix lk is known as the density matrix. There is an abstract operator corresponding to this matrix that is basis-independent. It can be seen that the operator = and similarly

Z 1X ~= Z j

=1 ( )

Z X

=1

( )

ih ih

( )

j j

( )

have matrix elements lk when evaluated in the basis set of vectors fj k ig.

h lj j k i =

Note that is a hermitian operator

Z X

=1

h lj

( )

ih

( )

j ki =

Z X

=1

( Cl( ) Ck

= lk

y=

so that its eigenvectors form a complete orthonormal set of vectors that span the Hilbert space. If wk and jwk i represent the eigenvalues and eigenvectors of the operator ~, respectively, then several important properties they must satisfy can be deduced. Firstly, let A be the identity operator I . Then, since hI i = 1, it follows that X 1 = 1 Tr( ) = Tr(~) = w

Thus, the eigenvalues of ~ must sum to 1. Next, let A be a projector onto an eigenstate of ~, A = jwk ihwk j Then hPk i = Tr(~jwk ihwk j) But, since ~ can be expressed as ~=

X

Pk .

k

X

wk jwk ihwk j

and the trace, being basis set independent, can be therefore be evaluated in the basis of eigenvectors of ~, the expectation value becomes

hPk i =

= However,

hwj j

i;j = wk

wi ij ik kj

1 hPk i = Z

Z X

=1

( )

jwk ihwk j

( )

Z 1X = Z jh

=1

( )

jwk ij2 0

P

Thus, wk 0. Combining these two results, we see that, since k wk = 1 and wk 0, 0 wk 1, so that wk satisfy the properties of probabilities. With this in mind, we can develop a physical meaning for the density matrix. Let us now consider the expectation value of a projector jai ihai j Pai onto one of the eigenstates of the operator A. The expectation value of this operator is given by 1 hPai i = Z

Z X

=1

( )

jPai j

( )

1 i= Z

Z X

=1

( )

jai ihai j

( )

1 i= Z

Z X

=1

jhai j

( ) 2

ij

( But jhai j ( ) ij2 Pai ) is just probability that a measurement of the operator A in the th member of the ensemble will yield the result ai . Thus,

1 hPai i = Z 3

P X

=1

Pa(i )

or the expectation value of Pai is just the ensemble averaged probability of obtaining the value ai in each member of the ensemble. However, note that the expectation value of Pai can also be written as

= =

X X

k;l k

k;l

Z 1 XhP ( ) i = X w jha jw ij2 k i k ai Z

=1

The interpretation of this equation is that the ensemble averaged probability of obtaining the value ai if A is measured is equal to the probability of obtaining the value ai in a measurement of A if the state of the system under consideration were the state jwk i, weighted by the average probability wk that the system in the ensemble is in that state. Therefore, the density operator (or ~) plays the same role in quantum systems that the phase space distribution function f (?) plays in classical systems.

The time evolution of the operator can be predicted directly from the Schrodinger equation. Since (t) is given by (t) = the time derivative is given by

Z @ =X @t =1 Z X

=1

( )

(t)ih

( )

(t)j

Z Xh Hj = i1 h

=1

@j @t

( )

(t)i h (t)i h

( )

(t)j + j (t)j ? j

( )

@ (t)i @t h

(t)h h

( )

(t)j

i

( )

( )

( )

( )

(t)jH

where the second line follows from the fact that the Schrodinger equation for the bra state vector h

@ = 1 H; ] @t ih

= i1 (H ? H ) h 1 H; ] =

ih

( )

Note that the equation of motion for (t) di ers from the usual Heisenberg equation by a minus sign! Since (t) is constructed from state vectors, it is not an observable like other hermitian operators, so there is no reason to expect that its time evolution will be the same. The general solution to its equation of motion is (t) = e?iHt=h (0)eiHt=h = U (t) (0)U y (t) The equation of motion for (t) can be cast into a quantum Liouville equation by introducing an operator 4

@ ?ih @t h

(t)j is

( )

(t)j = h

( )

(t)jH

What kind of operator is iL? It acts on an operator and returns another operator. Thus, it is not an operator in the ordinary sense, but is known as a superoperator or tetradic operator (see S. Mukamel, Principles of Nonlinear Optical Spectroscopy, Oxford University Press, New York (1995)). De ning the evolution equation for this way, we have a perfect analogy between the density matrix and the state vector. The two equations of motion are

We also have an analogy with the evolution of the classical phase space distribution f (?; t), which satis es with iL = f:::; H g being the classical Liouville operator. Again, we see that the limit of a commutator is the classical Poisson bracket.

At equilibrium, the density operator does not evolve in time; thus, @ =@t = 0. Thus, from the equation of motion, if this holds, then H; ] = 0, and (t) is a constant of the motion. This means that it can be simultaneously diagonalized with the Hamiltonian and can be expressed as a pure function of the Hamiltonian = f (H ) Therefore, the eigenstates of , the vectors, we called jwk i are the eigenvectors jEi i of the Hamiltonian, and we can write H and as

X X

H=

=

i i

1. The microcanonical ensemble

Although we will have practically no occasion to use the quantum microcanonical ensemble (we relied on it more heavily in classical statistical mechanics), for completeness, we de ne it here. The function f , for this ensemble, is

f (Ei ) E = (Ei ? (E + E )) ? (Ei ? E ) where (x) is the Heaviside step function. This says that f (Ei ) E is 1 if E < Ei < (E + E ) and 0 otherwise. The

partition function for the ensemble is Tr( ), since the trace of is the number of members in the ensemble: (N; V; E ) = Tr( ) =

X

(Ei ? (E + E )) ? (Ei ? E )] 5

The thermodynamics that are derived from this partition function are exactly the same as they are in the classical case:

S (N; V; E ) = ?k ln (N; V; E ) 1 = ?k @ ln T @E

N;V

etc.

2. The canonical ensemble

In analogy to the classical canonical ensemble, the quantum canonical ensemble is de ned by = e? H f (Ei ) = e? Ei Thus, the quantum canonical partition function is given by

X Q(N; V; T ) = Tr(e? H ) = e? Ei

and the thermodynamics derived from it are the same as in the classical case: A(N; V; T ) = ? 1 ln Q(N; V; T )

E (N; V; T ) = ? @@ ln Q(N; V; T ) @ P (N; V; T ) = 1 @V ln Q(N; V; T ) etc. Note that the expectation value of an observable A is

1 hAi = Q Tr(Ae? H ) Evaluating the trace in the basis of eigenvectors of H (and of ), we obtain X X hAi = 1 hE jAe? H jE i = 1 e? Ei hE jAjE i

i i i i

Q i

Q i

The quantum canonical ensemble will be particularly useful to us in many things to come.

3. Isothermal-isobaric and grand canonical ensembles

Also useful are the isothermal-isobaric and grand canonical ensembles, which are de ned just as they are for the classical cases: (N; P; T ) = dV e? PV Q(N; V; T ) = 0 1 1 X X

N =0

Z

dV Tr(e? (H +PV ) )

Z ( ; V; T ) =

e N Q(N; V; T ) =

N =0

Tr(e? (H ? N ) )

As a simple example of the trace procedure, let us consider the quantum harmonic oscillator. The Hamiltonian is given by P2 H = 2m + 1 m!2 X 2 2 and the eigenvalues of H are 1 En = n + 2 h!; n = 0; 1; 2; ::: Thus, the canonical partition function is

Q( ) =

1 X

This is a geometric series, which can be summed analytically, giving ? h!=2 1 1 Q( ) = 1e? e? h! = e h!=2 ? e? h!=2 = 2 csch( h!=2) The thermodynamics derived from it as as follows: 1. Free energy: The free energy is ? A = ? 1 ln Q( ) = h! + 1 ln 1 ? e? h! 2 2. Average energy: The average energy E = hH i is 3. Entropy The entropy is given by

? h! 1 E = ? @@ ln Q( ) = h! + 1h!ee? h! = 2 + hni h! 2 ?

n=0

1 X? e? h! n e? (n+1=2)h! = e? h!=2

n=0

? e? h! S = k ln Q( ) + E = ?k ln 1 ? e? h! + h! 1 ? e? h! T T

Now consider the classical expressions. Recall that the partition function is given by Thus, the classical free energy is 1 Q( ) = h dpdxe

Z

p2 1 2m + 2

m!2 x2

1=2 1 =h 2 m

m!

1=2

1 = 2!h = h!

In the classical limit, we may take h to be small. Thus, the quantum expression for A becomes, approximately, in this limit: AQ ?! h! + 1 ln( h!) 2

AQ ? Acl ?! h! 2 The residual h!=2 (which truly vanishes when h ! 0) is known as the quantum zero point energy. It is a pure quantum e ect and is present because the lowest energy quantum mechanically is not E = 0 but the ground state energy E = h!=2.

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