7.

/ What is the uncertainty in momentum if we wish to locate an electron within

an atom, say, so that ∆x is approximately 50 pm?
8. Show that eαx is an eigenfunction of the operator dn /dx n . What is the

-
Chem 156 Introduction to Quantum Chemistry eigenvalue?
∂
Problem Set for the First Exam 9. Show that eikx is an eigenfunction of the operator P̂x = −ih̄ ∂x . What is the
eigenvalue?
Dr. Gil C. Claudio
I
10. Determine whether or not the following pairs of operators commute

First Semester 2023-2024 Â B̂

d d2 d
(a) dx dx2
+ 2 dx
d
Reference (b) x dx
(c) SQR SQRT
• Donald A. McQuarrie, Quantum Chemistry 2nd ed., University Science ∂ ∂
(d) ∂x ∂y
Books, 2007.
7
11. Evaluate the commutator [ Â, B̂], where  and B̂ are given below
↳
1. Prove explicitly that
! ∞ ! ∞ (a) Â = d2
, B̂ = x
−αx2 −αx2 dx2
e dx = 2 e dx
d d
−∞ 0 (b) Â = dx − x, B̂ = dx
"x d
by breaking the integral from −∞ to ∞ into one from −∞ to 0 and another (c) Â = 0 dx, B̂ = dx
from 0 to ∞. Let z = − x in the first integral and z = x in the second to prove d2 d
the above relation. (d) Â = dx2
− x, B̂ = dx + x2

↳
2. By using the same procedure in Problem B-4, show explicitly that 12. The wavefunctions for a particle restricted to lie in a rectangular region of
/
lengths a and b (a particle in a two-dimensional box) are
! ∞ 2
xe−αx dx = 0 $1
ny πy
#
−∞ 4 2 n x πx
ψnx ny = sin sin
ab a b

-
3. Calculate the de Broglie wavelength for a baseball (0.5 oz) traveling at 90 mph. %
0 ≤ x ≤ a
4. Calculate the de Broglie wavelength of an electron traveling at 1.00% of the n x , ny = 1, 2, . . .
0 ≤ y ≤ b
speed of light.
Show that these wave functions are normalized.
/
5. Using the Bohr quantization condition

mvr = nh̄
↳
13. Suppose that a particle in a box is in the state prepared by the normalized state
function ⎧
⎨ ) 30 * 12
calculate the velocity of an electron in the first Bohr orbit. ψ( x ) = a5
x(a − x) 0≤x≤a
⎩ 0 otherwise
6. Calculate the uncertainty in the position of a baseball thrown at 90 mph if we
-
measure its speed to a millionth of 1.0 %.
↳
(a) Show that this wave function is normalized.

1
 /
,
(b) Calculate the energy of the system. 15. The eigenfunctions of a particle constrained to move on a circular ring of
radius a are
14. Show by direct calculation that σE2 = E2 − ⟨ E⟩2 = 0 for a particle in a box,
+ ,

for which -
2 nπx 1
ψn ( x ) = sin 0≤x≤a ψm (θ ) = √ eimθ where m = 0, ±1, ±2, . . . and 0 ≤ θ ≤ 2π
a a 2π
In other words, show that the only values of the energy that can be observed
are the energy eigenvalues,
n2 h2 where θ describes the angular positions of the particle about a ring. Prove that
En = these eigenfunctions form an orthonormal set. Note that e±ix = cos x ± i sin x
8ma2