Physical Chemistry Third Edition

(C. Jardin) #1

16.3 The Operator Corresponding to a Given Variable 693



  1. A hermitian operator has a set of eigenfunctions and eigenvalues.

  2. The eigenvalues of a hermitian operator are real.

  3. Two eigenfunctions of a hermitian operator with different eigenvalues are orthogonal
    to each other.

  4. Two commuting hermitian operators can have a set of common eigenfunctions.

  5. The set of eigenfunctions of a hermitian operator form a complete set for expansion
    of functions obeying the same boundary conditions.


EXAMPLE16.6

a.Show that the operatord/dxis linear.
b.Show that it is not hermitian.
Solution
a. d
dx

(f+g)
df
dx

+
dg
dx
d(cf)
dx

c
df
dx

b.We integrate by parts:
∫∞

−∞

f(x)∗

dg
dx
dxf(x)∗g(x)

∣∣



−∞


∫∞

−∞

g(x)

df∗
dx
dx

The functionsfandgmust vanish at the limits of integration, so we have
∫∞

−∞

f(x)∗
dg
dx

dx−

∫∞

−∞

df∗
dx

g(x)dx

which is the negative of what we would require for a hermitian operator.

The proofs for Properties 4 and 5 are in Appendix B. Property 5 involves
orthogonality. Two functionsfandgareorthogonalto each other if


f∗gdq


g∗fdq 0

(

definition of
orthogonality

)

(16.3-31)

where the integrals are taken over all values of the coordinates. The two integrals in
Eq. (16.3-31) are the complex conjugates of each other so that if one vanishes, so does
the other.

EXAMPLE16.7

Show that the first two energy eigenfunctions of the particle in a one-dimensional box of
lengthaare orthogonal to each other.
Solution
The energy eigenfunctions are found in Eq. (15.3-10). The formula contains a constantC,
which we assume to be real. Quantum mechanical integrals are taken over all values of the
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