I1 CLASSICAL PHYSICS

1. Hamilton's Equations(*)
The laws of classical mechanics can be formulated by describing a
system at a given instant through a set of general coordinates q, and
their conjugate momenta p,. For a system with "n degrees of freedom,"
the index i = 1, 2, . .. , n. For N masspoints, one has n = 3 N ; for
~llacroscopicsystems n is always a very large number, and in the case of
radiation, it is even infinite. The dynamical properties of the mechanical
system are specified by the energy expressed as a function of the variables
p, and 9,. This function is called the hamiltonian and shall be denoted
by

or, in abbreviated form,

H = H ( P ~qi)
,

where the symbols pi and q, will be used to indicate the two complete sets
of n variables p, and q,, respectively. A knowledge of the function H(p,, 9,)
is sufficient to yield the equations of motion in the form of Hamilton's
equations

= - dH
-dqi
dt ap,

for the time derivatives of each of the momenta and coordinates. Because
one thus deals with a system of first-order differential equations, the values
of the dynamical variables at a given time to lead upon integration to their
values at any other time t.
The simplest application of these equations is the motion of a non-
relativistic mass point in three dimensions. As general coordinates and
momenta we take the usual cartesian values
4 Fundamentals of Statistical Mechanics

The hamiltonian has the form

Hamilton's equations for the time derivative of the coordinates then give

dq* dH - 1
- =- - -Pi ; i = l , 2, 3
dt dp, m

The equations for the time derivative of the momenta are

which defines the it%omponent of the force. In vector notation these

equations read
p = mv

which are indeed Newton's laws.

As another important special case, Hamilton's equations include those
of newtonian mechanics for a material system of N masspoints. With the
notat ion
981 = Z s ; ~ = 1 ,2, ... 9 N

982 = V S particle label (1.10)

for the cartesian coordinates and

Psl = p,,
Ps2 = Psy
Ps3 = psz
 Fundamentals of Stat istical Mechanics 5

for the corresponding components of the momenta, the pair

Pea, Qea ; S = 1, 2, ...9 N

particle label

cartesian coordinates
thus stands for the pair p,, q, (i = 1, 2, . .. , 3N) in the previous notation,
applied to a system of n = 3 N degrees of freedom. The hamiltonian is
here the sum
H=T+V (1.13)
of the kinetic energy T(p) as a function of the momenta pea and of the
potential energy V(q) as a function of the coordinates qso The square of
the momentum for the sth particle is
3

and the kinetic energy is given by the expression

The potential energy V contains both the interactions between the

particles and the effects of the walls. We assume that V has the form

where a typical wall potential Vw can be sketched as in Figure 1.1.

Figure 1.1 A typical wall potential acting on a confined particle is

sketched in one dimension.
6 Fundamentals of Statistical Mechanics

The components f,, of the force acting on the mass point s are given by

dV
fea = --
%,a

Hamilton's equations for the time derivative of the components of

momenta in the present notation take the form

They are equivalent to the statement for vectors in Newton's mechanics

that the rate of change of momentum is equal to the force. On the other
hand, the form

of the second set of Hamilton's equations represents the relation between

the components of the velocity

and the components pea of the momentum. With T given by Eq.(1.15),

this relation can be written in the form

Pea = mevea (1.21)

in accordance with Newton's definition of the momentum as the product

of mass and velocity. A combination of these results yields

as the statement of Newton's law that the force is equal to the mass times
the acceleration.
As another application of Hamilton's equations, the previous examples
can be extended to describe relativistic motion of mass points if the single-
particle kinetic energy appearing in the hamiltonian is taken to have the
 Fundamentals of Statistical Mechanics 7

where mo is the rest mass of the particle and c is the velocity of light. In
this case the time derivative of the coordinate is given by

or, in vector notation,

cP
v= ,/-
This relation can be squared and inverted to give

The square root of this relation then gives

The validity of Eq.(1.21) in the relativistic case is seen to demand a

dependence of the mass on the velocity such that

where

The equation of motion is now again given by E q ~ ~ ( l .or

8 ) (1.18); in the
case of many particles, the mass and velocity carry a label s. One can go
over to the limiting case of zero rest mass mo = 0 with the result of the
contribution
T = cp
to the kinetic energy from Eq.(1.23) and velocity

from Eq.(1.25).
One advantage of Hamilton's equations is that they are invariant
against a large class of transformations. In fact, they follow from a
variational principle
,lrLdt =0
8 Fundamentals of Statistical Mechanics

with

and fixed endpoints so that

bp,(t)= 0 ; for t = tl and t = tz
(1.34)
b q i ( t )= 0
We treat bpi and bqi as independent variations. It follows from the Euler-
Lagrange equations that

-dp,
+--8 H - 0
dt dqi
Consider a general transformation

and an arbitrary function F ( p i , qi; p i , q ) . Then one also has

with L' defined by

Indeed, the variation of F is given b y

and therefore

since both 6qi, and bpi, and also

 Fundamentals of Statistical Mechanics 9

vanish for t = t l and t = t 2 [Eqs.(1.34)].

In order that Hamilton's equations hold in terms of the new variables
and new hamiltonian

with
H = H [ P ~ ( P9~ ,, c l i ( ~ k , qk)] = Hf(pk, 96) (1.43)
it is necessary that

Therefore

Transformations that leave the form of Hamilton's equations invariant are

said to be canonicall-
We illustrate these results with a point transformation, or coordinate
transformation

which forms a special case of the above. We may look for a transformation
with F = 0, in which case Eq.(1.46) reduces to

f The function F that generutes the canonical transformation through

Eqs.(1.38) and (1.44) can be generalized to include an explicit dependence
on the time t [see A. L. Fetter and J. D. Walecka, Theoretical Mechanics
of Particles and Continua, McGraw-Hill Book Co., New York (1980)l;
this extension is unnecessary for the present development.
10 Fundamentals of Statistical Mechanics

This equation is satisfied if the new momenta are defined by

We give two examples:

1. Transformation to polar coordinates in two dimensions.
Introduce the usual radial and polar coordinates in two dimensions.
The cartesian coordinates are given by

The new momenta are obtained immediately from Eq.(1.49)

The hamiltonian for a non-relativistic mass point moving in two dimen-

sions then takes the form (in an obvious notation)

Since the transformat ion is canonical, Hamilton's equations hold in terms

of the new general coordinates (r, 4).
2. Transformation to spherical coordinates in three dimensions.
The transformation of the cartesian coordinates to polar-spherical
coordinates in three dimensions is given by
x = r sin 0 cos q5
y = r sin0 sin 4 (1.53)

The new momenta are obtained from Eq.(1.49) according to

ax a9 dz
pe =PX-
de +pyz ++,-
ae = r(p, cos 8 COS 4 + p, cos 0 sin 4 - p, sin 0)
 Fundamentals of Statistical Mechanics 11

A combination of these results gives

Thus the hamiltonian for a non-relativistic mass point moving in three

dimensions takes the form

Again, since the transformation is canonical, Hamilton's equations hold

in terms of the new general coordinates (r, 8, 4).
Irrespective of the system considered, it is an important general
consequence of Hamilton's equations that the energy is a constant of
the motion. Indeed, due to the time-dependence of the momenta and
coordinates one has

~ H ( P, ,qi) = --
(aH dpi aH dq,
dt ap, dt + --)
aq* dt (1.57)

and hence from Eqs. (1.3)

In the preceding case dealing with a system of masspoints, this property

for the hamiltonian in Eqs.(l.l3-1.16) arises from the fact that Eq.(1.17)
demands that the force be derived from the gradient of the potential
energy. On the other hand, Newton's law Eq.(1.22) remains valid, for
example, upon inclusion of a frictional force proportional to the velocity,
which leads to a dissipation of energy in violation of Eq.(1.58). It might
seem, therefore, that Hamilton's equations are not sufficiently general
to allow for dissipative processes. One has to remember, however, that
any such process is accompanied by the development of heat. In fact,
the macroscopic conservation of energy, postulated by the first law of
thermodynamics, is in essence based upon the recognition of heat as a
form of energy. Regarded, instead, from the microscopic point of view, the
purely mechanical energy remains conserved even in frictional processes,
with the difference, however, that here it goes over from an ordered
12 Fundamentals of Stat istical Mechanics

to a disordered form in the nature of molecular motion. One of the

important goals of statistical mechanics is to generally clarify in what
sense a part of the total mechanical energy is understood to correspond
to the macroscopic concept of heat.
Both in thermodynamics and in pure mechanics the energy of a system
re~nainsconstant in the absence of external influences, but can otherwise
be made to increase or decrease. Whereas the first law postulates such
a change of energy to be additively composed of the amount of heat
transferred to the system and of the work performed upon it, only
the latter point can be readily expressed in mechanical terms. Indeed,
Eq.(1.58) loses its validity if the hamiltonian depends not only on the
dynamical variables, but also explicitly upon the time so that Eq.(1.2) is
to be replaced by
H = H(p,, q,, t) (1.59)
With the time derivatives of p, and q, still given by Eqs.(l.3), it now
follows that instead of Eq.(1.58) one has

Specifically, this result applies when the hamiltonian is considered as a

function of the internal variables pi and q, as well as of some external
parameters, to be denoted by Ej ( j= 1,2, . . ., m). Writing thus

where cj stands for the set of parameters t j ( j= 1 , 2 , . . . , m), and letting

theso parameters depend upon the time, one obtains from Eq.(1.60)

The differential change of H during the time interval dt can thus be

written in the form
d H = 6W (1.63)
where
aH
6w = Cq d t j
j=l
(1.64)

is to be recognized as the differential work performed by external agents

in order to change the parameters by the amount gjyj. The symbol 6W,
rather than dW, is used in Eqs.(1.63-1.64) to indicate that the righthand
 Fundamentals of Stat istical Mechanics 13

side of Eq.(1.64) does not represent a total differential of the hamiltonian

given by Eq.(1.61). The appearance of work as force times distance can
be formally maintained by considering the quantities as coordinates
external to the system and the quantities

as the components of a generalized force against which the work has to

be performed, so that one can write
m

As an example, one may consider a single paxameter 6 to signify the

position of a m~vablepiston of area A, used to vary the volume V of a gas
in a cylindrical^ container (Figure 1.2). In the hamiltonian of Eqs.(l.lf
1.16), the effect of the piston, like that of the fixed walls of the container,
is described by a sum of terms Vw in the potential energy that increase
sharply with small distances of a molecule from the inner surface (Figure
1.1). The parameter E here locates the position of the potential Vw due
to the surface of the piston. The molecules in the close vicinity of this
surface are repelled, and the forces of reaction result in a total force f,
exerted from the inside upon the piston. With the definition p s f /A of
the pressure as force per unit area and with dV = Ad< for the differential
change of volume, the expression 6 W = -f dc from Eq.(1.66) assumes
the familiar form
6W = -pdV (1.67)
for the differential work required to change the volume of the gas.

Figure 1.2. A gas is confined to a volume by a movable piston. Work is

achieved by the change of an external parameter, in this case the position
of the piston 6, which locates the position of the wall potential Vw.