Chem 3412 Physical Chemistry II Fall 2017, Quantum Chemistry, Exam 1

Name:_________________________________Date: 9/27/2017

I have adhered to the GT Honor code: ________________________(signed)

Instructor: R. M. Dickson
You may use a calculator and 8.5” x 11” sheet of notes (1 side)
Show your work, state any assumptions.

Constants and conversions:

Planck's Constant: h = 6.626 x 10-34 Joule·seconds

ℏ = 1.05457 x 10-34 Joule·seconds

Boltzmann Constant: kb = 1.3807 x 10-23 Joule/K

mass of proton: mp = 1.67 x 10-27 kg

mass of electron: me = 9.109 x 10-31 kg

1 electron Volt (eV) = 1.6 x 10-19 Joules

Electron charge = 1.6 x 10-19 Coulombs

Potentially useful integrals and derivatives are on the last page of this exam
2 Exam1-Fall2017-key.nb

1. (30 points total) Explain the meaning of the following mathematical expressions
(1-2 sentences at most, neatly written).
ℏ
A) σ x σ px ≥
2

x and px are related by an uncertainty relation. They are conjugate

variables. Both x (position) and momentum cannot be simultaneously
measured. Measurement of position changes measurement of
momentum. momentum and position operators do not share a
common set of eigenfunctions any combination of these is fine.

Et
B) Ψ[q, t] = ψ[q] ⅇ (Ψ and ψ are our wavefunctions describing the quantum system)
-ⅈ
ℏ

The potential governing particle motion is time independent

only depends on spatial coordinates. The wavefunction
can be separated into space and time - dependent parts.
 Exam1-Fall2017-key.nb 3

b
C)  ψ [x] ψ[x] ⅆ x
*
a

This is the probability of finding the particle between x = a and x = b.

ψ* ψ is the probability density. Integrating
this over volume gives the probability of finding a particle
in the region of space defined by the limits on the integral.
4 Exam1-Fall2017-key.nb

2) (45 Points total) A (free) particle moving on a circular ring with fixed radius
r, can be described by the wavefunction ψm[ϕ] = A Exp[ⅈ m ϕ], where ϕ is an
angular coordinate (see figure). Because of circular boundary conditions, ψ[ϕ]]=
ψ[ϕ+2π], m must be an integer. Note: This is still very similar to a particle in a 1D
box - just that the box is circular. The potential on the ring is 0, the potential off
the ring is ∞.

)
A. (15 points) If the angular momentum operator is Lz = -ⅈ ℏ ∂
∂ϕ
, What is the
average angular momentum for a given state m? Please show your work.

5 points. One needs to normalize the wavefunction, so at least set this up with the proper limits (0 to 2 π)
2π
Assumingm ∈ Integers, SolveA2  Exp[- ⅈ m ϕ] Exp[ⅈ m ϕ] ⅆ ϕ ⩵ 1, A
0

1 1
A → - , A → 
2π 2π

10 points for setting up the proper integral (the expectation value with angular momentum operator
sandwiched inbetween the wavefunctions, proper limits, normalization constant) and calculation of the
final value.
1 2π
In[70]:= -  Exp[- ⅈ m ϕ] ⅈ ℏ ∂ϕ Exp[ⅈ m ϕ] ⅆ ϕ
2π 0

Out[70]= mℏ

B. (10 points) Although the wavefunctions have a similar form, and they are both 1-
D systems, what is the essential difference between the particle on a ring and the
free particle that makes one a good wavefunction and the other not?

Answer: because the particle on a ring is bound, it is normalizable. The free particle is not normalizable
(not square integrable as it has probability of being found everywhere. The free particle therefore is not
a good wavefunction. The particle on a ring wavefunction is.

C. (5 points) Based on the picture given at the beginning of the problem, what is
the physical significance of the sign of the parameter m?

Answer: it is the sense of rotation. Just like the free particle, the sign of k was the direction of motion
(the momentum). Here the “free particle” is bound to stay on the ring and it can rotate in either direction.
This changes the sense of angular momentum (right hand rule... either up or down).
 Exam1-Fall2017-key.nb 5
C. (5 points) Based on the picture given at the beginning of the problem, what is
the physical significance of the sign of the parameter m?

Answer: it is the sense of rotation. Just like the free particle, the sign of k was the direction of motion
(the momentum). Here the “free particle” is bound to stay on the ring and it can rotate in either direction.
This changes the sense of angular momentum (right hand rule... either up or down).

D. 15 points Calculate the uncertainty of Lz. What

does this tell you about the uncertainty in angle ? Explain

3 points indicate what the proper standard deviation operator is

σlz = (lz - < lz >)2 = < lz >2 - < lz2 >

(7 points) Calculate the integrals and determine the value (ideally showing more
steps than this...)

1 2π 1 2π 2
 Exp[- ⅈ m ϕ] ⅈ ℏ ⅈ ℏ ∂ϕ ∂ϕ Exp[ⅈ m ϕ] ⅆ ϕ -  Exp[- ⅈ m ϕ] ⅈ ℏ ∂ϕ Exp[ⅈ m ϕ] ⅆ ϕ
2π 0 2π 0

(5 points) Any of the following text is fine for explanation:

There is no uncertainty in angular momentum (Because of how the problem is set up, there is only a z-
component of angular momentum in this problem, so the z-component is the total angular momentum....
hence the Lz notation... not an important part of this answer). The wavefunction is an eigenfunction of
the angular momentum operator, giving the same result every time for a system in state m. Therefore
there is no spread of values, and no uncertainty. Because of the uncertainty relation between angular
momentum and angle, there is infinite uncertainty about angle - we have no information about angle
because angular momentum is perfectly defined.
ℏ
ΔL Δϕ ≥
2
Here, ΔL = 0, so

ℏ ℏ
Δϕ ≥ = = ∞
2 ΔL 0
6 Exam1-Fall2017-key.nb

3) (25 points total) Let’s consider an experiment of putting a larger particle in a

box that has applications to quantum computing and Bose-Einstein condensates.
Treat a single potassium atom confined to a 1-D box of length L= 1x10-7 m as a
particle in a box.
A) (15 points) Compute the energy of the 39K atom in the ground (n=1) state of
the 1D box. What temperature would need to be reached for the n=1 state to be
distinguishable from the n=2 state? (in other words, what are the energies of the
n=1 and n=2 states, and to what temperature does this difference correspond?)
Express the answers in SI (kg, m, s, J, K, ...) units. Show your work and state any
assumptions.

(5 points) Start with the particle in a box energies as a function of n:

h2 n2
<n =
8 m a2
or
ℏ2 π2 n2
<n =
2 m a2

realize that the mass is that of the potassium atom of interest. For part A,
it is 39 AMU. Convert using constant from front page.

The energy difference between these states is a

bunch of constants times the difference in n2 for each level

5 points for calculating the energies

of both states and getting their differences
2
6.626 × 10-34 
Δ< = 22 - 12  (*this is in Joules*)
-7 2
8 × 39 × 1.67 × 10 -27
10 

2.52786 × 10-28

(5 points) Use Boltzmann’s constant (front page) to convert between energy (J)
and Kelvin to determine the temperature to which this energy difference
corresponds.
Δ<  1.38 × 10-23  (*because Boltzmann's constant has units of J/K, this is now K*)
0.0000183178

18 microKelvin

B) (10 points) What if a different isotope of potassium, 41K , was trapped

instead? What temperature would this need to be cooled to? Explain why any
differences arise.
 Exam1-Fall2017-key.nb 7

B) (10 points) What if a different isotope of potassium, 41K , was trapped

instead? What temperature would this need to be cooled to? Explain why any
differences arise.
(5 points for realizing the only thing that changes is the mass, then calc the ener-
gies) Here, only the mass of the atom changes from 39 AMU to 41 AMU.
2
6.626 × 10-34 
Δ< = 22 - 12 (*this is in Joules*)
-7 2
8 × 41 × 1.67 × 10 -27
10 

2.40455 × 10-28

Δ<  1.38 × 10-23 

0.0000174243

This temperature is 17 microKelvin.

(5 points for a reasonable explanation)

The lower temperature needed to separate the states for 41 K vs 39 K is because the lighter mass object
will have higher energy states and higher differences in energy levels (inverse relationship on mass). It
is harder to cool heavier atoms and get them all in the same state.
8 Exam1-Fall2017-key.nb

Potentially useful integrals and derivatives:

Cos[b x] Sin[b x]
 Sin[b x] ⅆ x = -  Cos[b x] ⅆ x =
b b
2
x Sin[2 b x] 2
Sin[2 b x] x
 Sin [b x] ⅆ x = -  Cos [b x] ⅆ x = +
2 4b 4b 2
ⅆ ⅆ
Sin[b x] = b Cos[bx] Cos[b x] = - bSin[bx]
ⅆx ⅆx

bx
ⅇb x ⅆ
ⅇ ⅆx = ⅇb x = b ⅇb x
b ⅆx

bx
ⅇb x (b x - 1) cos2 (b x)
xⅇ ⅆx =  Cos[b x] Sin[b x] ⅆ x = -
b2 2b
Sin[2 b x] x Cos[2 b x]
 x Cos[b x] Sin[b x] ⅆ x = -
8b 2 4b
bx 2 2
ⅇ b x - 2 b x + 2
2 bx
 x ⅇ ⅆx =
b3
1 - 2 b2 x2  Cos[2 b x] + 2 b x Sin[2 b x]
2
 x Cos[b x] Sin[b x] ⅆ x =
8 b3
Sin[b x] x Cos[b x]
 x Sin[b x] ⅆ x = -
b2 b
Cos[b x] x Sin[b x]
 x Cos[b x] ⅆ x = +
b2 b

2
Cos[2 b x] x Sin[2 b x] x2
 x Sin [b x] ⅆ x = - - +
8 b2 4b 4
2
2
Cos[2 b x] x Sin[2 b x] x
 x Cos [b x] ⅆ x = + +
8b 2 4b 4
2 2
2 x Sin[b x] b x - 2 Cos[b x]
2
 x Sin[b x] ⅆ x = -
b2 b3
2 x Cos[b x] b2 x2 - 2 Sin[b x]
2
 x Cos[b x] ⅆ x = +
b2 b3
x Cos[2 b x] 2 b2 x2 - 1 Sin[2 b x] x3
2 2
 x Sin [b x] ⅆ x = - - +
4 b2 8 b3 6
x Cos[2 b x] 2 b2 x2 - 1 Sin[2 b x] x3
2 2
 x Cos [b x] ⅆ x = + +
4 b2 8 b3 6
∞
-b x 2 π ∞
2 -b x 2 π
 ⅇ ⅆx =  x ⅇ ⅆx =
-∞
b -∞ 2 b3/2