Quantum Chemistry – Solution set 1

1. Complex number algebra

2. Simple differential equations
3. Interference of light
4. The photoelectric effect
5. De-Broglie assumption
6. Bohr model

1. Complex numbers
∗
a. Present the complex number 𝑧 = √2(−2 − √2𝑖) as a complex exponent

∗
𝑧 = √2(−2 − √2𝑖) = −2√2 + 2𝑖
𝑟 = √8 + 4 = √12
2 1
𝜃 = tan−1 (− ) = tan−1 (− ) , 2nd quadrant
2√2 √2

1
𝑖(tan−1 (− )+𝜋+2𝜋𝑛)
𝑧 = √12𝑒 √2
𝜋 𝜋
Notice that the arctan will always give us a value in the range [− 2 , 2 ], in a
case that the point is either in the third or second quadrant, we should
add 𝜋 to correct it
b. Present the following complex numbers in Cartesian coordinates:
𝑖𝜋 ∗
√2 ( )
i. 𝑧1 = 2
𝑒 3

(𝑒 𝑖𝑥 −𝑒 −𝑖𝑥 )
ii. 𝑧2 = 2
𝑖𝜋 ∗
√2 ( ) √2 𝜋 𝜋 √2 √3
𝑧1 = 2
𝑒 3 = 2
(cos ( 3 ) − 𝑖 ⋅ 𝑠𝑖𝑛 ( 3 )) = 2
(0.5 − 𝑖 2
),

(𝑒 𝑖𝑥 − 𝑒 −𝑖𝑥 ) 1 1
𝑧2 = = [(cos 𝑥 + 𝑖 sin 𝑥) − (cos 𝑥 − 𝑖 sin 𝑥)] = ⋅ 2𝑖 sin 𝑥
2 2 2
= 𝑖 sin 𝑥
2
c. Calculate the following |𝐴𝑒 𝑖𝜑 |
The square of the absolute value of a complex number is its product with its
2 ∗
conjugate: |𝐴𝑒 𝑖𝜑 | = (𝐴𝑒 𝑖𝜑 ) ⋅ (𝐴𝑒 𝑖𝜑 ) = |𝐴|2 𝑒 𝑖𝜑 ⋅ 𝑒 −𝑖𝜑 = |𝐴|2 , many
times we assume 𝐴 is real and we will not use the absolute notation, still this
form is more general.

2. Simple differential equations

a. Define the term “ordinary nth-order linear homogeneous differential
equation with constant coefficients”, Give example and a counter
example for each of the terms (ordinary, linear,
homogeneous, differential, and constant coefficients)
linear homogeneous differential equation for 𝑦 = 𝑦(𝑥), n>m
𝑑𝑛 𝑑𝑚
𝑎 𝑛𝑦+𝑏 𝑚𝑦+𝑦 = 0
𝑑𝑥 𝑑𝑥
  “Differential” means that the equation contains the derivatives of
the unknown functions as opposed to algebraic equation, e.g.
𝑦 = 𝑥2 + 2
 “Linear” means that only 𝑦 and its derivatives appear and not a
𝑑𝑛 2 𝑑𝑚
power or product of them as opposed to 𝑎 (𝑑𝑥 𝑛 𝑦) + 𝑏 𝑑𝑥 𝑚 𝑦 +
√𝑦 = 0
 “Ordinary” means that only total derivatives with respect to 𝑥 appear
in the equation, as opposed to a function of both position and time
𝜕𝑦 𝜕𝑦
𝑦(𝑥, 𝑡) with an equation 𝜕𝑡 + 𝜕𝑥 = 0 (which is called partial)
 “Homogeneous” means that there is not a free term that doesn’t
𝑑𝑛 𝑑𝑚
include 𝑦 as opposed to 𝑑𝑥 𝑛 𝑦 + 𝑏 𝑑𝑥 𝑚 𝑦 + 𝑦 = 2𝑥 5
 “nth-order” means that highest derivative is of order n
 “Constant coefficients” means that 𝑎 and 𝑏 are constant factors as
𝑑𝑛 𝑑𝑚
opposed to 𝑥 2 𝑑𝑥 𝑛 𝑦 + 𝑥 𝑑𝑥 𝑚 𝑦 + 𝑦 = 0
b. Solve the following ODE’s:
Hint: For each ODE you can substitute the solution 𝑦 = 𝐴𝑒 𝑟𝑥 With
constant 𝑟 ) to build a characteristic polynomial where 𝑟 𝑛 substitutes
𝑑𝑛
𝑑𝑥 𝑛
𝑦. We solve the algebraic equation to find the solutions 𝑟1 , 𝑟2 , …

The solutions of the ODE will be a linear combination of 𝑒 𝑟1 𝑥 , 𝑒 𝑟2 𝑥 , … . If

to solutions are degenerate (𝑟1 = 𝑟2 ) the terms 𝑒 𝑟1 𝑥 and 𝑥𝑒 𝑟1 𝑥 are the
solutions of the equation.
𝑑2
i. 𝑑𝑥 2
𝑦
− 4𝑦 = 0
𝑟 − 4 = 0 → 𝑟1,2 = ±2 → 𝑦 = 𝐴𝑒 2𝑥 + B𝑒 −2𝑥 where A and be
2

can be any numbers

𝑑2
ii. 𝑑𝑥 2
𝑦 + 4𝑦 = 0
𝑟 + 4 = 0 → 𝑟1,2 = ±2𝑖 → 𝑦 = 𝐴𝑒 2i𝑥 + B𝑒 −2i𝑥 where A and be
2

can be any numbers

iii. 2𝑦′′ − 3𝑦′ − 2𝑦 = 0
x
1
2𝑟 2 − 3𝑟 − 2 = 0 → 𝑟1,2 = − 2 , 2 → 𝑦 = 𝐴𝑒 −2 + B𝑒 2𝑥 where A
and be can be any numbers
𝑑2 𝑑
iv. 𝑑𝑥 2
𝑦
− 2 𝑑𝑥 𝑦 + 𝑦 = 0
𝑟 − 2𝑟 + 1 = 0 → 𝑟1,2 = 1 → 𝑦 = 𝐴𝑒 𝑥 + Bx𝑒 𝑥 where A and be
2

can be any numbers

c. For each of the solutions, substitute your solution and show that it
satisfies the equation
3. The two slits interference experiment (first performed by Thomas Young in 1801)
was, at its time an argument for the theory that light is a wave:

In this experiment, a coherent light source of wavelength 𝜆 is projected through two

slits (of infinitesimal width) at distance 𝑑 of each other
a. Find the phase difference accumulating as a function of 𝜃, the angle on a
distant (𝐿 ≫ 𝑑, far-field approximation) screen.
The light is coherent. The different distances are the cause of phase
2𝜋
difference Δ𝐿 = 𝑑 ⋅ sin(𝜃) and the phase accumulated is 𝜑 = 𝑘Δ𝐿 = 𝜆
𝑑 ⋅
sin(𝜃), two plots are presented to support this calculation:

b. Calculate the light intensity as a function of 𝜃

The wave amplitude is the sum of waves coming from the two different slits:
𝜓 = 𝐴𝑒 𝑖(𝑘𝑥−𝜔𝑡) + 𝐴𝑒 𝑖(𝑘𝑥−𝜔𝑡+𝜑) = 𝐴𝑒 𝑖(𝑘𝑥−𝜔𝑡) (1 + 𝑒 𝑖𝜑 )
The intensity is 𝐼 = |𝜓|2 = 𝐴2 ⋅ (1 + 𝑒 𝑖𝜑 + 𝑒 −𝑖𝜑 + 1) = 2𝐴2 (1 + cos(𝜑))
2𝜋
= 2𝐴2 (1 + cos ( 𝑑 ⋅ sin(𝜃)))
𝜆
c. Find the location of minimum intensity
2𝜋
The minimum is at cos ( 𝜆 𝑑 ⋅ sin(𝜃)) = −1:
2𝜋
𝑑 ⋅ sin(𝜃) = π + 2𝜋𝑚; 𝑚 = 0, ±1, ±2, …
𝜆
1
(𝑚 + 2) 𝜆
sin(𝜃) =
𝑑
d. Find the location of maximum intensity
2𝜋
The maximum is at cos ( 𝜆 𝑑 ⋅ sin(𝜃)) = 1:
 2𝜋
𝑑 ⋅ sin(𝜃) = 2𝜋𝑚; 𝑚 = 0, ±1, ±2, …
𝜆
𝑚𝜆
sin(𝜃) =
𝑑

4. Photoelectric effect
Mercury spectrum lines in the wave-length region 2302Å to 3130Å 𝑤ere used to
study the photoelectric effect by irradiating the metallic surfaces of Aluminum and
Zinc.
The following table gives the required voltage (in volts) to suppress the photoelectric
current for different wave-lengths and metals

a. Calculate the value of Planck's constant

b. Calculate the Work function of the two metals (Energy needed to extract an
electron from the metal)

In the photoelectric effect the energy needed to stop electrons (voltage times the
electron charge) is equal to the kinetic energy it has after leaving the metal surface:
𝐸𝑘 = ℎ𝜈 − Φ where ℎ𝜈 is the energy of a photon according to Einstein relation and
Φ is the work needed to separate an electron from the surface ( specific to any
metal).
𝑐 Å
It is easier to work with frequencies 𝜈 = 𝜆 where 𝐶 = 3 × 1018 𝑠 and kinetic energy
𝐸𝑘 = 𝑉 ∗ 𝑒 where 𝑒 = 1.602 × 10−19 𝑐𝑜𝑢𝑙𝑜𝑚𝑏

𝜈 [𝐻𝑧] 𝐸𝑘 , 𝑍𝑛 [J] 𝐸𝑘 , 𝐴𝑙 [𝐽]

1.18E+15 2.86E-19 3.01E-19
1.13E+15 2.51E-19 2.66E-19
1.01E+15 1.73E-19 1.88E-19
9.60E+14 1.39E-19 1.54E-19

We plot the data for aluminium as an example:

 3.5E-19

Ek [J] 3.0E-19

2.5E-19

2.0E-19

1.5E-19

1.0E-19
y = 6.6E-34x - 4.8E-19
5.0E-20 R² = 1.0E+00
0.0E+00
5.0E+14 1.5E+15
ν [Hz]

So we see
ℎ = 6.6 × 10−34 𝐽𝑠
Φ = 4.8 × 10−19 𝐽
For the units of ℎ:
[𝑦 𝑎𝑥𝑖𝑠 𝑢𝑛𝑖𝑡𝑠] 𝐽
[ℎ] = 𝑢𝑛𝑖𝑡𝑠 𝑜𝑓 𝑠𝑙𝑜𝑝𝑒 = = −1 = 𝐽𝑠
[𝑥 𝑎𝑥𝑖𝑠 𝑢𝑛𝑖𝑡𝑠 ] 𝑠

5. De-Broglie assumption: A particle has wave-length (just like light) that corresponds
ℎ
to its momentum: 𝑃𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒 = 𝜆 = ℏ𝑘
We will use the relations for momentum and kinetic energy:
𝑚𝑣 2 𝑝2
𝐸𝑘 = = → 𝑝 = √2𝑚𝐸𝑘
2 2𝑚
ℎ ℎ ℎ
And for wave-length: 𝜆 = = = .
𝑝 𝑚𝑣 √2𝑚𝐸𝑘
𝑚
a. Find the wavelength of a gun bullet (1000 𝑠
, 30 𝑔𝑟) and determine
whether it presents quantum behavior
ℎ 6.626 ∙ 10−34𝐽𝑠
𝜆= = = 2.2 ∙ 10−35 𝑚 = 2.2 ∙ 10−26 𝑛𝑚
𝑚𝑣 30 ⋅ 10−3 𝑘𝑔 ∙ 103𝑚/𝑠
Therefore, we can't measure its quantum character.
b. An electron is accelerated over 100𝑉. Find its wavelength and determine
whether it presents quantum behavior
The kinetic energy of a particle accelerated over 100𝑉 is 𝐸𝑘 = 𝑉 ⋅ 𝑞 =
𝐽
100 𝐶 ⋅ 1.60 ⋅ 10−19 𝐶
ℎ ℎ 6.626 ∙10−34 𝐽𝑠
And for an electron 𝜆 = 𝑝 = = =
√2𝑚𝑒 𝐸𝑘 𝐽
√2∗9.1𝑒−31 𝑘𝑔∗100 ⋅1.60⋅10−19 𝐶
𝐶

0.123𝑛𝑚
This is much larger than an electron therefore it will show significant
quantum behavior
c. A Hydroxide ion (𝑂𝐻 − ) is accelerated over 100𝑉. Find its wavelength and
determine whether it presents quantum behavior
 for a Hydroxide ion (𝑂𝐻 − ) 𝑚 = 17 ∗ 1836 ∗ 9.1𝑒 − 31 𝑘𝑔 , the charge is
1.60 ⋅ 10−19 𝐶
ℎ ℎ
𝜆= =
𝑝 √2𝑚𝑝 𝐸𝑘
6.626 ∙ 10−34𝐽𝑠
=
√2 ∗ 17 ∗ 1836 ∗ 9.1𝑒 − 31 𝑘𝑔 ∗ 100 𝐽 ∗ 1.60 ⋅ 10−19 𝐶
𝐶
= 6.95 × 10−13 m = 0.6𝑝𝑚
The size of such a particle is of the order of 100𝑝𝑚, and therefore its
behavior is completely classical
6. A Hydrogen-like atom (unknown atomic number, only a single electron) emits the
following wave-length, determine its nuclear charge and to which state does its
electronic state relax (we assume that all lines represent a decay to the same level)
304.3,256.8,243.4,237.7,234.7,233.0, wavelength in angstrom
ℎ𝑐
First lets calculate the energy released by each emission line, Δ𝐸 = ℎ𝜈 = 𝜆
, using
−15 18
ℎ = 4.14 × 10 eV s, 𝑐 = 3 × 10 𝑎𝑛𝑔𝑠𝑡𝑟𝑜𝑚/𝑠
𝛥𝐸 =40.8, 48.4, 51.0, 52.2, 52.9, 53.3,𝑒𝑉

Now we use Bohr model to calculate the energy levels of the first 4 atoms:
𝑚𝑒 𝑍 2 𝑒 2 𝑍2 𝑅𝐸
𝐸𝑛 = − 2ℏ2 𝑛2
=− 𝑛2
where Rydberg energy: 𝑅𝐸 = 13.606 𝑒𝑉
𝑍 2 𝑅𝐸
Δ𝐸𝑛→1 = 𝐸1 − 𝐸𝑛 = 𝑍 2 𝑅𝐸 (1 − )
𝑛2

z=1 z=2 z=3 z=4

ΔE2→1 10.20 40.82 91.84 163.27
ΔE3→1 12.09 48.38 108.85 193.51
ΔE4→1 12.76 51.02 114.80 204.09
ΔE5→1 13.06 52.25 117.56 208.99
ΔE6→1 13.23 52.91 119.05 211.65
ΔE7→1 13.33 53.31 119.95 213.25
Now we can see that the differences match a decay of electron to level 1 in an atom
with 𝑍 = 2.
7. Calculate the number of photons emitted in 4 𝑠 by a lamp of 10𝑊 which radiates
1% of its energy as monochromtic light with wavelength 6000 Å (orange light)
𝑐
, hence, a frequency 𝜈 = ,
𝜆
 𝑒𝑟𝑔
8. A beam of light with wavelength 6500 Å and energy 106 𝑠
arrives at a
photoelectric cell. This energy is entirely used to produce photoelectrons. Calculate
the intensity of the electric current which flows in the electric circuit connected to
the photoelectric cell.