(Taken from Quantum Chemistry by Donald A.

McQuarrie, 2nd Edition)

Quantum Chemistry

Exercises October 05 2017

1. Which of the following candidates for wave functions are normalizable over the indicated
intervals?

Normalize those that can be normalized. Are the others suitable wave functions?

2. In this problem, we will prove that the form of the Schrodinger equation imposes the
condition that the first derivative of a wave function be continuous. The Schrdinger
equation is

If we integrate both sides from a - to a + , where a is an arbitrary value of x and

is infinitesimally small, then we have

Now show that is continuous if V(x) is continuous.

Suppose now that V (x) is not continuous at x = a, as in
 Show that

so that d/dx is continuous even if V(x) has a finite discontinuity. What if V(x) has an
infinite discontinuity, as in the problem of a particle in a box? Are the first derivatives of
the wave functions continuous at the boundaries of the box?

3. Determine whether the following functions are acceptable or not as state functions over
the indicated intervals.

x a; 0 y
4. Consider a free particle constrained to move over the rectangular region 0
b. The energy eigenfunctions of this system are

The Hamiltonian operator for this system is

Show that if the system is one of its eigenstates, then

5. Suppose that a particle in a two-dimensional box is in the state

Show that (x, y) is normalized, and then calculate the value of E associated with
the state described by (x, y).

6. Show that

are orthonormal over the interval - < x < .

7. Show that the set of functions {(2/a)1/2

cos(nx/a)}, n=0, 1, 2, ..., is orthonormal over the
interval 0 x a.

8. Evaluate the commutator [ , B], where and B are given below.

9. Show that

and

10. We shall define the operators:

 and

Show that

and that

11. Consider a particle in a two-dimensional box. Determine ,

and

12. Can the position and total angular momentum of an electron be measured
simultaneously to arbitrary precision?

13. If n is an eigenfunction of the time-independent Schrodinger equation, then

Show that if m ( x) and

n ( x) are both stationary states of , then the state

satisfies the time-dependent Schrodinger equation.

14. Show that the momentum operator is Hermitian. Use the fact that

15. Which of the following operators is Hermitian: i d/dx, d2 /dx2 , i d2 /dx2 ? Assume that the
functions on which these operators operate are appropriately well behaved at infinity

16. Consider a particle moving in the potential energy

 whose mathematical form is

where V0 is a constant.

Show that if E > V0 then the solution to the Schrdinger equation in the two regions (1
and 2) are:

and

where

represents a particle traveling to the right and e-ikx

As we know, eikx represents a particle
traveling to the left. The physical problem we wish to set up is a particle of energy E
traveling to the right and incident on a potential barrier of height V0. If we wish to exclude
the case of a particle traveling to the left in region 2, we set D = 0 in equation 2. The
squares ofthe coefficients in equations 1 and 2 represent the probability that the particle
is traveling in a certain direction in a given region. For example, | A |2 is the probability
that the particle is traveling with momentum +k1 in the region x < 0. If we consider many
particles, N0, instead of just one, then we can interpret | A |2 N0 to the number of particles
 with momentum +k1 in the region x < 0. The number of these particles that pass a given
|2 N0 , where the velocity v is given by k1/m.
point per unit time is given by v| A
Now apply the conditions that (x) and d (x)/dx must be continuous at x = 0 to obtain

A + B = C
and

k1 (A - B) = k2 C
Now define a quantity

And show that

Similarly define

And show that

The symbols r and t stand for reflection coefficient and transmission coefficient,
respectively. Give a physical interpretation of these designations. Show that r + t = 1.
Would you have expected the particle to have been reflected even though its energy, E,
is greater than the barrier height, V0? Show that r 0 and t 1 as V0 0.

17. In this problem, we introduce the idea of quantum-mechanical tunneling, which plays a
central role in such diverse processes as the decay of nuclei, electron-transfer
reactions, and hydrogen bonding. Consider a particle in the potential energy regions as
shown below.

Mathematically, we have

Show that if E < V0, the solution to the Schrodinger equation in each region is given by

and

where

If we exclude the situation of the particle coming from large positive values of x , then F =
0 in equation 3. Argue that the transmission coefficient, the probability the particle will get
past the barrier, is given by

Now use the fact that ( x) and d ( x)/dx must be continuous at x = 0 and x = a to obtain

A + B = C + D i k1 ,(A - B) = k2 (C - D) (6)

and
Eliminate B from equations 6 to get A in terms of C and D. Then solve equations 7 for C
and D in terms of E. Substitute these results into the equation for A in terms of C and D
to get the intermediate result

Now use the relations sinh x = (ex - e-x )/2 and cosh x = (ex + e-x )/2 to get

Now multiply the right side by its complex conjugate and use the relation c osh2 x = l +
sinh2 x to get

Finally, use the definition of k1 and k2 to show that the probability the particle gets through
the barrier (even though it does not have enough energy!) is

or

a2 E / 2 , and =E/V0 = /v0. Next figure shows a plot of t

Where v0 = 2 m a2 V0 / 2 , = 2 m
versus for v0= 10. To plot t versus for values of > 1, you need to use the relation
sinh i x = i sin x. What would the classical result look like?