CHEM 352: Examples for chapter 1.

1. The ground state wavefunction for a hydrogen atom is 0 (r) = 1 3 er/a0 .

a0

(a) What is the probability for finding the electron within radius of
a0 from the nucleus?
(b) Two excited states of hydrogen atom are given by the following
wavefunctions:
2ar 2ar
1 (r) = A(2 + r)e 0 and 2 (r) = Br sin() cos()e 0

Proceed in the following order: 1) obtain from the orthogo-

nality requirement between 0 and 1 , 2) use the normalization
requirement sepratately for 1 and 2 to get constants A and B,
respectively.
Solution:

(a) The probability P for finding the electron within a0 (a ball with
radius a0 ; denoted by V below) is:

Z Za0
1 2
P = 0 0 d = 3 e2r/a0 |4r
{z dr}
a0
V 0 =d

4 a30 5a30 e2
= = 1 5e2 0.323
a30 4

Note that the 4 in the volume element above comes from the
fact that the function in the integral does not depend on the an-
gles and and therefore the angular part can be integrated
independently to yield 4 (i.e. the original volume element d =
r2 sin()dddr is then effectively just 4r2 dr). Above we have
used the following result from a tablebook:

Z  
2 ax aax 2 2x 2
x e dx = x + 2
a a a

1
 This was applied in the following form:

Za0
e2r/a0 r2 dr
0
 
e2r/a0 2 2r 2 1 2
= r + 2

2/a0 2/a0 (2/a0 ) 2/a0 (2/a0 )2
 
a0 e2 a2 a3
= a20 + a20 + 0 + 0
2 2 4
3 2 3 3 3 2
5a e a a 5a0 e
0 + 0 = 0
4 4 4

(b) First recall the wavefunctions:

1
0 (r, , ) = p 3 er/a0
a0
1 (r, , ) = A(2 + r)er/(2a0 ) , 2 (r, , ) = B sin() cos()rer/(2a0 )

First we calculate from the orthogonality:

Z Z Z
4A
1 0 d = 4 1 (r)0 (r)r2 dr =p 3 (2 + r)e3r/(2a0 ) r2 dr = 0
a0
0 0
Z
(2 + r)e3r/(2a0 ) r2 dr = 0
0
Z Z
3r/(2a0 ) 2
2 e r dr + e3r/(2a0 ) r3 dr = 0
0 0
16a30 96 4
2 + a =0
27 81 0
1
a30 + a40 = 0 =
a0

Then determine A from the normalization condition:

2
 Z Z Z2
|1 (r, , )|2 r2 sin()drdd
r=0 =0 =0
Z  2
2 r
= 4A 2 er/a0 r2 dr
a0
r=0

Z Z Z
4 1
= 4A2 4 r2 er/a0 dr r3 er/a0 dr + r4 er/a0 dr
a0 a20
r=0 r=0 r=0

 
2! 2 4 3! 1 4!
= 4A 4 3
4
+ 2
(1/a0 ) a0 (1/a0 ) a0 (1/a0 )5


= 4A2 8a30 24a30 + 24a30 = 32A2 a30 = 1
1 1
A= p 3
= p
32a0 4 2a30

B can also be determined from normalization:

Z Z Z2
|2 (r, , )|2 r2 sin()drdd
r=0 =0 =0
Z Z Z2
= B2 r4 er/a0 dr sin3 ()d cos2 ()d
r=0 =0 =0
 
24 4 1
B2 = 32B 2 a50 = 1 B = p
(1/a0 )5 3 32a50
1
= p
4 2a50

Above we have used the following integrals (tablebook):

3
 Z
n!
xn eax dx =
an+1
Z0
cos(3ax) 3 cos(ax)
sin3 (ax)dx =
12a 4a
Z
x sin(2ax)
cos2 (ax)dx = +
2 4a

2. (a) Which of the following functions are eigenfunctions of d/dx and

d2 /dx2 : exp(ikx), cos(kx), k, and exp(ax2 ).
(b) Show that the function f (x, y, z) = cos(ax) cos(by) cos(cz) is an
eigenfunction of the Laplacian operator () and calculate the cor-
responding eigenvalue.
(c) Calculate the standard deviation r for the ground state of hy-
drogen atom 0 (r).
e 2
(d) Calculate the expectation value for potential energy (V (r) = 4 0r
)
in hydrogen atom ground state 0 (r). Express the result finally
in the units of eV.
Solution:

d(eikx )
(a) dx
= ikeikx = constant original function. Thus this is
an eigenfunction of the given operator.
d2 (eikx d
dx2
= dx (ikeikx ) = k 2 eikx = constantoriginal function.
Thus this is an eigenfunction of the given operator.
d(k) 2
dx
= ddx(k)
2 = 0. This could be considered as en eigenfunction

with zero eigenvalue.

2
d(eax ) 2
dx
= 2axeax 6= constant original function, thus not
an eigenfunction.
2 ax2
d2 (eax )
= d(2axe ) 2
dx2 dx
= 2a(2ax2 + 1)eax 6= constant original
function, thus not an eigenfunction.
d(cos(kx))
dx
= k sin(kx). Not an eigenfunction.

4
 d2 (cos(kx))
dx2
= d(k sin(kx))
dx
= k 2 cos(kx). This is an eigenfunc-
tion (with eigenvalue k 2 ).
(b) f (x, y, z) = cos(ax) cos(by) cos(cz). The partial derivatives are:
f (x, y, z)
= a sin(ax) cos(by) cos(cz)
x
f (x, y, z)
= b cos(ax) sin(by) cos(cz)
y
f (x, y, z)
= c cos(ax) cos(by) sin(cz)
z
and
2 f (x, y, z)
= a2 cos(ax) cos(by) cos(cz)
x2
2 f (x, y, z)
= b2 cos(ax) cos(by) cos(cz)
y 2
2 f (x, y, z)
2
= c2 cos(ax) cos(by) cos(cz)
z
Therefore f (x, y, z) = (a2 + b2 + c2 )f (x, y, z) = constant
original function and this is an eigenfunction with the corre-
sponding eigenvalue (a2 + b2 + c2 ).
(c) The standard deviation can be calculated as:
1
0 (r) = p er/a0
a30
Z

2 1 4 3a50
r = 3 e2r/a0 r2 |4r 2
{z dr} = = 3a20
a0 a30 4
0 d
Z
1 2 3a0
hri = e2r/a0 r |4r
{z dr} =
a30 2
0 d

9a20
hri2 =
4

2 9a2 4a2
r hri2 = 3a20 0 = 0
q 4 4
3
hr2 i hri2 = a0 0.87a0
2

5
 (d) The potential energy expectation can be calculated as:
1 e2
0 (r) = p 3 er/a0 and V (r) =
a0 40 r
Z Z
D E e2 1 2 e 2
V = 2 3 e2r/a0 |4r dr = e2r/a0 rdr
4 0 a0 r {z } 0 a30
r=0 d r=0
2
e a20 e 2
= 3
= 27.2 eV
0 a0 4 40 a0

1
4 2 /2
3. Consider function (x) =
ex . Using (only) this function,
show that:

(a) Operators x and px do not commute.

(b) Operators x2 and the inversion operator I commute (Ix
= x).

Note that consideration of just one function does not prove a given
property in general.
Solution:

(a)
 1/4 2 /2
(x) = ex

d
px = ih and [x, px ] (x) = (xpx px x) (x)
dx
To obtain the commutator, we need to operate with x and px :
 1/4 d  1/4
x2 /2 2
(xpx ) (x) = ih x e = ih x2 ex /2
dx
 1/4 d  2

(px x) (x) = ih xex /2
dx
 1/4 2
 1/4 2
= ih x2 ex /2 ih ex /2

When these are subtracted, we get:

6
  1/4 2 /2
(xpx ) (x) (px x) (x) = ih ex

When the wavefunction (x) is removed, we have:

[x, px ] = ih

Because the commutator between these operators is non-zero, it

means that they are complementary.
(b) The commutator for the given function is:
h i    1/4 2
x, I (x) = x2 I Ix2 ex /2

 1/4 2
 1/4 2
= x2 e(x) /2 (x)2 e(x) /2

 1/4 2
 1/4 2
= x2 ex /2 x2 ex /2 = 0

2
x and I commute for the given function.

4. A particle is described by the following wavefunction: (x) = cos()k (x)

+ sin()k (x) where is a parameter (constant) and k and k are
orthonormalized eigenfunctions of the momentum operator with the
eigenvalues +hk and hk, respectively.

(a) What is the probability that a measurement gives +hk as the

momentum of the particle?
(b) What is the probability that a measurement gives hk as the
momentum of the particle?
(c) What wavefunction would correspond to 0.90 probability for a
momentum of +hk?
(d) Consider another system, for which = 0.91 + 0.42 + c3 3 .
Calculate c3 when 1 , 2 and 3 are orthonormal. Use the nor-
malization condition for .

Solution:

7
 (a) The probability for measuring +hk is cos2 (). We have a su-
perposition of the eigenfunctions of momentum and therefore the
squares of the coefficients for each eigenfunction give the corre-
sponding probability.
(b) The probability for measuring hk is sin2 ().
(c) Given cos2 () = 0.90 (hence cos() = 0.95) we use the nor-
malization condition cos2 () + sin2 () = 1 where we solve for
sin() = 0.32. The overall sign for the wavefunction does not
matter and therefore we have two possibilities for our wavefunc-
tion: = 0.95eikx 0.32eikx .
(d) Normalization condition: 1 = (0.9)2 +(0.4)2 +c23 . Thus c3 = 0.17.

5. Consider a particle in the following one-dimensional infinitely deep box

potential: 
0, when |x| a
V (x) =
, when |x| > a
Note that the position of the potential was chosen differently than in
the lectures. The following two wavefunctions are eigenfunctions of the
Hamiltonian corresponding to this potential:
1  x  1  x 
1 (x) = cos and 2 (x) = sin
a 2a a a

with the associated eigenvalues are E1 = 1 eV and E2 = 4 eV. Define

a superposition state as = 12 (1 + 2 ).

(a) What is the average energy of the above superposition state (e.g.
< H >)?
(b) Plot 1 and 2 and determine the most probable positions for a
particle in these states.
(c) What are the most probable
q positions for the particle given by
2


wavefunction 3 (x) = L
sin 3x
L
where the box potential is
now located between [0, L].

Solution:

8
(a) We calculate the expectation value (H1 = E1 1 and H2 =
E2 2 ):
D E Z
H = (x)H(x)dx
Z
1
= (1 (x) + 2 (x)) H (1 (x) + 2 (x)) dx
2

Z
1 1
= (1 (x) + 2 (x)) (E1 1 (x) + E2 2 (x)) dx = (E1 + E2 )
2 2
= 2.5 eV

(b) For a = 1 both 1 (x) (one maximum) and 2 (x) (maximum and
minimum) are shown below:

The most probable values for position can be obtained from the
squared wavefunctions:

1 has the maximum value at r = 0 whereas 2 has two maxima at

0.5. Note that on average both will give an outcome of hri = 0.
(c) The most probable positions are given by the square of the wave-
function 0 (x) = (2/L)1/2 sin(3x/L). The probability function

9
 is then |0 (x)|2 sin2 (3x/L). The extremum points for this
function can be obtained by:
d

sin2 (3x/L) = 0 sin(3x/L) cos(3x/L) = 0
dx  
3x 3x 1
= n or = n+
L L 2
n n + 1/2
x = L or x = L
3 3
Second derivatives can be used to identify the extrema:
   
d2 2

3x 3x
sin (3x/L) cos2 sin 2
dx2 L L
At x = n3 L the values are positive which means that these cor-
respond to (local) minima. For x = n+1/23
L the values are nega-
tive and these points correspond to (local) maxima. For example,
when L = 2 the probability function looks like:

6. Calculate the uncertainty product px for the following wavefunc-

tions:

1/2

(a) n (x) = a2 sin nx
a
with 0 x L (particle in a box)
 2

(b) n (x) = Nv Hv ( x) exp x2 (harmonic oscillator)

Solution:

10
(a) For momentum:
 1/2  nx 
2
n (x) = sin , where 0 x L
L L
ZL  1/2  nx     1/2  nx 
2 d 2
hpx i = sin ih sin dx
L L dx L L
0 | {z } | {z } | {z }
n
(x) px n (x)

ZL  nx  d   nx 
2ih
= sin sin dx
L L dx L
0

ZL  nx   nx 
2nih
= sin cos dx = 0
L2 L L
|0 {z }
=0
ZL  1/2  nx   2  1/2  nx 

2 2 d 2
px = sin ih sin dx
L L dx L L
0 | {z } | {z } | {z }
n
p2x n

ZL
2h2  nx  d2  nx 
= sin sin dx
L L dx2 L
0
ZL
2n2 2 h2  nx   nx  n2 2 h2
= sin sin dx =
L3 L L L2
0
| {z }
=L
2

q
Now we can calculate p = hp2x i hpx i2 = nh
L
. For position

11
 we have:
ZL  1/2  nx   2 1/2  nx 
2
hxi = sin x sin dx
L L L L
0
ZL  nx 
2 2
= x sin dx = L/2
L L
0
ZL  1/2  nx   2 1/2  nx 

2 2 2
x = sin x sin dx
L L L L
0
ZL  
2 2 2
 nx  L2 (2 2 n2 3) L2 3
= x sin dx = = 1 2 2
L L 6 2 n2 3 2 n
|0 {z }
L3 (4n2 2 6)
=
24 2 n2

q q
q
2 2 2
Now x = hx i hxi = L3 1 232 n2 L4 = L 12
2 1
212 n2 .
Since we have both x and p, we can evaluate the uncertainty
product: r
n2 2 6
px = h
12 12
The smallest value is obtained with n = 1: px 0.568h > h2 .
(b) First recall that:

2 1  1/4
n (x) = Nv Hv x ex /2 , where Nv =
2v v!

Also the following relations for Hermite polynomials are used (lec-
ture notes & tablebook):

Hv+1 = 2yHv 2vHv1

Z 
y 2 0, if v 6= v
Hv (y)Hv (y)e dy = v
2 v!, if v = v

12

Denote y = x and hence dy = dx. Now hxi is given by:
Z
2

x2 /2
x2 /2
hxi = Nv Hv x e xHv x e dx

Z
Nv2 2 /2 2 /2
= Hv (y)ey yHv (y)ey dy


Z
Nv2 2
= Hv (y)y Hv (y)ey dy = 0
| {z }
= 1 Hv+1 (y)+vHv1 (y)
2

The last two steps involved using the recursion relation for Her-
mite polynomials as well as their orthogonality property. Next we
calculate hx2 i:

Z

2 Nv2 2
x = 3/2 (yHv (y))2 ey dy


Z  2
Nv2 1 2
= 3/2 Hv+1 (y) + vHv1 (y) ey dy
2

 
Nv2 2v+1 (v + 1)! 2 v1
= 3/2 + v 2 (v 1)!
4
   
1 1 1 h 1
= ((v + 1) + v) = v+ = v+
2 2 k 2
q

Combining the above calculations gives x = v + 21 hk . Next
we calculate p:
d
p = ih and dy = dx.
dx
Z  
y 2 /2 y 2 /2
hpi = Nv Hv (y)e p Nv Hv (y)e dy

Z
2 /2 d  2

= ihNv2 Hv (y)ey Hv (y)ey /2 dy
dx

13
Above differentiation of the eigenfunction changes parity and there-
fore the overall parity of the integrand is odd. Integral of odd
function is zero and thus hpi = 0. For hp2 i we have:
Z

2 2 /2 2 /2 dy
p = Nv Hv (y)ey p2 Nv Hv (y)ey

The operator
must also be transformed from x to y: p2 = (ihd/dx)2
= (ih d/dx)2 ). The above becomes now:
Z  
y 2 /2 2 d2 2
 dy
Nv Hv (y)e h 2 Nv Hv (y)ey /2
dy

Z
2
y 2 /2 d2  y 2 /2

= h Nv2 Hv (y)e Hv (y)e dy
dy 2


Z
2
= h2 Nv2 Hv (y) (y 2 1)Hv (y) 2yHv (y) + Hv (y) ey dy

| {z }
=2vHv (y)
Z
  2
= h2 Nv2 Hv (y) (y 2 1)Hv (y) 2vHv (y) ey dy


Z Z
2

2 2

Nv2 (2v 1) Hv2 (y)ey dy + y 2 Hv2 (y)

= h ey dy
| {z }
2
| {z } =( 2 Hv+1 (y)+vHv1 (y))
1

= 2v v!
 
2
1 v+1
= h Nv2
(2v 1) 2 v! + v
2 (v + 1)! + v 2 2v1 (v 1)!
4
   
2
2
v v+1 v 2 1
= h Nv 2 v! 2v + 1 = h v +
2 2 2
 
1
= h mk v +
2

14
 q  
Therefore we have p = h mk v + 21 . Overall we then have
q
q  
xp = 1 h
v + 2 mk h mk v + 21 = h(v + 21 ) h2 .

7. Scanning tunneling microscopy (STM) is a technique for visualizing

samples at atomic resolution. It is based on tunneling of electron
through the vacuum space between the STM tip and the sample. The
tunneling current (I ||2 where is the electron wavefunction) is
very sensitive to the distance between the tip and the sample. Assume
that the wavefunction for electron tunneling
q through the vacuum is
given by (x) = B expKx with K = 2me (V E)/h2 and V E =
2.0 eV. What would be the relative change in the tunneling current I
when the STM tip is moved from x1 = 0.50 nm to x2 = 0.60 nm from
the sample (e.g. I1 /I2 = ?).
Solution:

The current is proportional to the square the wavefunction (|(x)|2 ):

I |(x)|2 = B 2 e2Kx
I1
= e2K(x1 x2 )
I2
1/2

K = 2me (V E) /h2
| {z }
=2 eV
 1/2
2(9.11 1031 kg)(2.0 eV)(1.602 1019 J/eV)
=
(1.0546 1034 Js)2
2K(x1 x2 ) = 2K (0.10 109 m) 1.45
I1
4.3
I2

8. Show that the sperhical harmonic functions a) Y0,0 , b) Y2,1 and c) Y3,3
are eigenfunctions of the (three-dimensional) rigid rotor Hamiltonian.
What are the rotation energies and angular momenta in each case?

15
 Solution:

h2 2
H(r, , ) = E(r, , ) where H =
2I
1 2 1
2 = 2 2
+ sin()
sin () sin()

2
Since h2I is constant, it is sufficient to show that spherical harmonics
are eigenfunctions of 2 . We operate on the given spherical harmonics
by 2 .

(a) 2 Y00 (, ) = 2 21 = 0 (no angular dependency). The rotation

2
energy is E = h2I 0 = 0. Also L2 = 0 h2 L = 0 (since
L2 = h2 2 ).
(b) 2 Y21 (, ) = ...differentiation... = 6Y21 (, ). The rotation

2 2
energy is E = h2I (6) = 3hI . Also L2 = 6 h2 L = 6h.
(c) Expression for Y33 was not given in the lecture

notes. We use Max-
3 5 7e3i sin3 ()
ima to obtain the expression: Y3 (, ) =
8 5
. Then we
need to evaluate: Y3 (, ) = ...differentiation... = 12Y33 (, ).
2 3
2
From this we can get the rotational energy as E = 6hI . Also

L2 = 12 h2 L = 12h.

9. Calculate the z-component of angular momentum and the rotational

kinetic energy in planar (e.g. 2-dimensional; rotation in xy-plane) rota-
tion for the following wavefunctions ( is the rotation angle with values
between [0, 2[):

(a) = ei
(b) = e2i
(c) = cos()
(d) = cos()ei + sin()ei

Solution:

16
 2 2 2
The Hamiltonian for 2-D rotation is H = L2Iz = h2I dd
2 where the

rotation axis is denoted by z and is the angle of rotation.

d i
(a) Operate first by Lz on ei : Lz ei = ih d e = hei . Thus Hei =
h2 i
2I
e .
d 2i
(b) The same reasoning gives: Lz e2i = ih d e = 2he2i and
4h2 2i
He2i = 2I
e .
(c) The given wavefunction is not an eigenfunction of Lz : Lz cos() =
ih ( sin()) (expectation value is zero). However, it is an eigen-
2
d2 h2
function of H: H cos() = h2I d 2 cos() = 2I cos().

(d) Operation by Lz would change the plus sign in the middle of the
wavefunction into a minus, hence this is not an eigenfunction of
i
Lz . It is an eigenfunction of H: H(cos()e

+ sin()ei ) =

2 2
h2I (i)2 cos()ei + (i)2 sin()ei = h2I cos()ei + sin()ei .

17