48 CHAPTER 3. HAMILTONIAN MECHANICS
where pressure P (V,T)=−∂F/∂V and entropy S(V,T)=−∂F/∂T are dependent vari-
ables. Likewise, enthalpy H(P, S)=U + PV and Gibbs free energy G(T,P)=H − TS
are introduced by Legendre transformations whenever one chooses (P, S) and (T,P), re-
sp ectively, as independent variables.
3.3 Hamiltonian Optics and Wave-Particle Duality*
Historically, the Hamiltonian method was first introduced as a formulation of the dynamics
of light rays. Consider the following phase integral
Θ[z]=
Z
t
2
t
1
[ k ·
˙
x − ω(x, k; t)]dt, (3.7)
where Θ[z] is a functional of the path z(t)=(x(t), k(t)) in ray phase space, expressed in
terms of the instantaneous position x(t) of a light ray and its associated instantaneous wave
vector k(t); here, the dispersion relation ω(x, k; t) is obtained as a root of the dispersion
equation det D(x,t; k,ω) = 0, and a dot denotes a total time derivative:
˙
x = dx/dt.
Assuming that the phase integral Θ[z] acquires a minimal value for a physical ray orbit
z(t), henceforth called the Principle of Phase Stationarity δΘ = 0, we can show that Euler’s
First Equation lead to Hamilton’s ray equations
dx
dt
=
∂ω
∂k
and
dk
dt
= −∇ω. (3.8)
The first ray equation states that a ray travels at the group velocity while the second ray
equation states that the wave vector k is refracted as the ray propagates in a non-uniform
medium (see Chapter 1). Hence, the frequency function ω(x, k; t) is the Hamiltonian of
ray dynamics in a nonuniform medium.
It was Prince Louis Victor Pierre Raymond de Broglie (1892-1987) who noted (as a
graduate student well versed in Classical Mechanics) the similarities between Hamilton’s
equations (3.2) and (3.8), on the one hand, and the Maupertuis-Jacobi (2.1) and Euler-
Lagrange (2.8) Principles of Least Action and Fermat’s Principle of Least Time (1.1) and
Principle of Phase Stationarity (3.7), on the other hand. By using the quantum of action
¯h = h/2π defined in terms of Planck’s constant h and Planck’s energy hypothesis E =¯hω,
de Broglie suggested that a particle’s momentum p be related to its wavevector k according
to de Broglie’s formula p =¯h k and introduced the wave-particle synthesis based on the
identity S[z]=¯h Θ[z] involving the action integral S[z] and the phase integral Θ[z]:
Particle Wave
phase space z =(q, p) z =(x, k)
Hamiltonian H(z) ω(z)
Variational Principle I Maupertuis −Jacobi Fermat
Variational Principle II Euler − Lagrange Phase − Stationarity