Physical Chemistry Exam 1 Key
Physical Chemistry Exam 1 Key
Physical Chemistry Exam 1 Key
Name:_________________________________Date: 9/27/2017
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
Et
B) Ψ[q, t] = ψ[q] ⅇ (Ψ and ψ are our wavefunctions describing the quantum system)
-ⅈ
ℏ
b
C) ψ [x] ψ[x] ⅆ x
*
a
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
Assumingm ∈ Integers, SolveA2 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).
(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
ℏ ℏ
Δϕ ≥ = = ∞
2 ΔL 0
6 Exam1-Fall2017-key.nb
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.
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
2.40455 × 10-28
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