2

Table of Contents
Necessity: 4

Asymmetry 4

Intuition: 4

Description: 5

Proposition: 5

Formulation: 6
Energy equivalence identity in Hamiltonian 6
Wave function: 7
Energy-frequency identity: 7
Collectively: 7

Normalization: 8
Proposition: 8
Case analysis: 9
Formulation: 10
Proposition: 11
Continuation: 11
Separation of Time-space components: 11
Time component solution: 11
Spatial component solution: 11
Explanation for coordinate transformation 12
Separation of Radial and angular components: 13
Computation table: 13
Continuation: 13
Separation of Polar and Angular equations: 14
Proposition: 14
Computation Table 14
Continuation 14
Polar and angular equations 14
Azimuthal equation 15
Solution analysis 15
Magnetic quantum number 16
Polar equation: 16
Proposition: 16
Azimuthal, Subsidiary/subshell quantum number condition: 17
Continuation 17
Radial equation: 17
Case:1 17
Case:2 18
Case:3 18
 3

Proposition: 18
Overall: 19
Normalization of radial term: 20
Energy quantisation: 21

Wave equation for hydrogen: 23

Case analysis: 24

Formulation: 25

Explanation of unsolvability: 25
Famous approximation methods: 25

N-electron system schrodinger equation 26

Computation of ground state of Helium 26

Formulation 26
Proposition: 26
Proposition: 26
A electron: 26
B electron: 27
Variational Method 27
Summary 27
Proposition 29
Perturbation Theory: 30
Proposition: 30
Verdict: 30

Multi-Electron system wave functions: 31

Slater determinant: 31
Intuition and derivation: 31
 4

Introduction:
Necessity:
The universe is composed of atoms. To understand how the world functions, we must have
to understand it by the very depth by which it is constituted. Physics is often regarded as the
mother of science because it can describe nearly everything in reality which is out of the
scope of other subjects. Quantum Mechanics is the branch of physics which explains the
motion of Atoms and subatomic particles and their behavior. Through that, we have gained
knowledge and insight of how chemical reactions and chemistry occurs. In Chemistry,
several exceptions can be seen to arise out of nowhere but if studied computationally, it will
seem obvious why the issue has been raised in the first place.

Asymmetry
It differs from Classical physics by a lot of extent. Due to its complexity, unpredictability and
the scale it is on. The behavior of atomic particles experimentally does not show any relation
to the macroscopic objects. Due to such, very weird wave-particle duality can be observed.
The introduction of the black body radiation problem, and the problems like photoelectric
effect also further supports this claim.

Intuition:
The main vital point of this branch is the introduction of Schrodinger’s wave equation.
Although it is nonrelativistic, still due to it, we can study the nature of atoms. The Paul-dirac
equation turned the schrodinger’s equation to relativistic by adding a relativistic term in it.

This equation is later turned to solve the atomic wave function. Also along with the energy
they are composed of. Through them, we can study the motion and thermodynamics of the
atomic system. The two most vital and necessary information for predicting the element.

Although, it is to be noted that it is analytically impossible to find out the solution for atoms
which have a multi-electron system.

So, we need to make some approximate methods in order to obtain the closest value of the
energy state of the element.

Several Mathematical entities were introduced in order to shorten/elaborate the explanation

regarding atomic nature.

Nevertheless, the possibilities and the technology we have achieved by studying this field is
paramount to any other field of science.
 5

Schrodinger Wave Equation:

Description:
Erwin Schrödinger postulated this equation in 1926. This equation was developed after the
discoveries and observations of the Rutherford and Bohr atomic model. The idea is simple,
to develop an equation with the following postulates:
● The object must move in wave-like motion.
● The motion of the object is dependent on the energy of the object

This equation, although it was sought to be the purpose for the atomic model, can actually
be applied to any particle if they follow the postulates mentioned above.

The yellow line indicates a photon being absorbed and the blue line indicates the jump of the
particle to a higher state.

Proposition:
Êψ(𝑥, 𝑦, 𝑧, 𝑡) = Ĥψ(𝑥, 𝑦, 𝑧, 𝑡)

[Here, `Ê` is the “energy operator” and `Ĥ` is the “Hamiltonian operator”]
[“Mathematical Operator” is an entity which executes (a/series of) mathematical operation(s) upon the mathematical entity it is
acting at. Generally all Mathematical operator’s instructions are defined]
[`x,y,z` are their respective axes values for the î, ĵ, ǩ components respectively]
[`t’ represents “Time”]
[“The Hamiltonian operator” is “Summation of kinetic and potential energy” of a particle]
 6
[“The energy operator” defines all the energy of a particle or a system.]

Formulation:

Energy equivalence identity in Hamiltonian

𝐸=𝐻
⇒ 𝐸 = 𝐸𝑘 + 𝐸𝑝
[Energy = E][Kinetic energy = 𝐸𝑘][Potential energy = 𝐸𝑝]
1 2
⇒𝐸 = 2
𝑚𝑢 + 𝑣
1 2
[𝐸𝑘 = 2
𝑚𝑢 ][𝐸𝑝 = 𝑣]
2
𝑝
⇒𝐸 = 2𝑚
+𝑣
2
𝑝 1 2
[𝑝 = 𝑚𝑣][ 2𝑚 = 2
𝑚𝑣 ][Hamiltonian form]
2
𝑝
⇒ 𝐸ψ = 2𝑚
ψ + 𝑣ψ
[Multiply both sides by our wave function]
[This is in fact the one dimensional equivalent to our schrodinger equation without any vector components and operators]

⇒ Êψ(𝑥, 𝑦, 𝑧, 𝑡) = ( 1
2𝑚
2
ṕ + 𝑣(𝑥, 𝑦, 𝑧, 𝑡) ψ(𝑥, 𝑦, 𝑧, 𝑡) )
[Expanding the Hamiltonian operator][Here, `ṕ` is the “momentum operator”]
[`∇` is called “Nabla operator”. It takes the partial derivative of all 3 components of its operand 3D vector function ]
მ მ მ
[∇ = მ𝑥
, მ𝑦
, მ𝑧
]
[It is to be especially noted that, as “Nabla operator” is a vector operator which operates on a vector, thus the resultant value is
also in vector]
−34 ℎ
[ṕ = − 𝑖ħ∇][𝑖 = − 1][ħ = 1. 054571817... ×10 𝐽𝑠][ħ = 2π
]
−34
[ℎ = 6. 62607004 × 10 𝐽𝑠]

⇒ Êψ(𝑥, 𝑦, 𝑧, 𝑡) = ( 1
2𝑚
2
(− 𝑖ħ∇) + 𝑣(𝑥, 𝑦, 𝑧, 𝑡) ψ(𝑥, 𝑦, 𝑧, 𝑡) )
( )
2
ħ 2
⇒ Êψ(𝑥, 𝑦, 𝑧, 𝑡) = − 2𝑚
∇ + 𝑣(𝑥, 𝑦, 𝑧, 𝑡) ψ(𝑥, 𝑦, 𝑧, 𝑡)

⇒ Êψ(𝑥, 𝑦, 𝑧, 𝑡) = (− )
2
ħ
2𝑚
∇ · ∇ + 𝑣(𝑥, 𝑦, 𝑧, 𝑡) ψ(𝑥, 𝑦, 𝑧, 𝑡)
[Here, ` . ` represents the dot product of two vector]

( )
2
ħ მ მ მ მ მ მ
⇒ Êψ(𝑥, 𝑦, 𝑧, 𝑡) = − 2𝑚
(( მ𝑥 , მ𝑦
, მ𝑧
) · ( მ𝑥 , მ𝑦
, მ𝑧
)) + 𝑣(𝑥, 𝑦, 𝑧, 𝑡) ψ(𝑥, 𝑦, 𝑧, 𝑡)

⇒ Êψ(𝑥, 𝑦, 𝑧, 𝑡) = (− )
2
ħ მ მ მ მ მ მ
2𝑚
( მ𝑥 მ𝑥
+ მ𝑦 მ𝑦
+ მ𝑧 მ𝑧
) + 𝑣(𝑥, 𝑦, 𝑧, 𝑡) ψ(𝑥, 𝑦, 𝑧, 𝑡)

( )
2 2 2 2
ħ მ მ მ
⇒ Êψ(𝑥, 𝑦, 𝑧, 𝑡) = − 2𝑚
( 2 + 2 + 2 ) + 𝑣(𝑥, 𝑦, 𝑧, 𝑡) ψ(𝑥, 𝑦, 𝑧, 𝑡)
მ𝑥 მ𝑦 მ𝑧
[This equation is in your book]
 7

Wave function:

𝑖(𝑥)
𝐼(𝑥) ≡ 𝑒 = 𝑐𝑜𝑠(𝑥) + 𝑖𝑠𝑖𝑛(𝑥)
[Any wave can be divided into sine and cosine waves/functions]
{“If you plot the movement of the electron with respect of time, you’ll find an oscillating wave” }
𝑖(α𝑥)
⇒ 𝐼(α𝑥) ≡ 𝑒 = 𝑐𝑜𝑠(α𝑥) + 𝑖𝑠𝑖𝑛(α𝑥)
𝑖(𝑘𝑥−ω𝑡)
⇒ 𝐼(𝑘𝑥 − ω𝑡) ≡ 𝑒 = 𝑐𝑜𝑠(𝑘𝑥 − ω𝑡) + 𝑖𝑠𝑖𝑛(𝑘𝑥 − ω𝑡)

𝑖(𝑘𝑥−ω𝑡)
Ѱ(𝑥) ≡ 𝑒
2π 2π
[𝑘 = λ
⇒λ = 𝑘
][ω = 2π𝑓]
{“ `x` is our particle’s displacement/position ”}
{“ `t` is the time of our wave function”}
{“ `k` is our wavelength and ‘ω` is our wave’s angular velocity ”}
[You may wonder, I have depicted a wave function of one dimension only, but our wave function above represents a full 3
dimensional object. You have to remember that time is also a component of a function. So, the differentiation of the particle with
respect to time will always stay the same regardless of any spatial dimensions]

მ მ 𝑖(𝑘𝑥−ω𝑡)
⇒ მ𝑡
[Ѱ(𝑥)] = მ𝑡
[𝑒 ]
[Taking derivative with respect to ‘t’ of both sides]
⇒ მ𝑡Ѱ(𝑥) = − 𝑖ωѰ(𝑥)

Energy-frequency identity:
𝐸 = ħω
[From Einstein’s photoelectric effect theory:]
𝐸 = ℎ𝑓
ℎ
⇒𝐸 = 2π
× 2π × 𝑓
⇒ 𝐸 = ħω

⇒ 𝐸Ѱ = ħωѰ
𝑖 𝑖
⇒− ħ
× 𝐸Ѱ =− ħ
× ħωѰ
𝑖
⇒− ħ
𝐸Ѱ = − 𝑖ωѰ
𝑖
⇒− ħ
𝐸Ѱ = მ𝑡Ѱ(𝑥)
−ħ
⇒ 𝐸Ѱ = მ Ѱ(𝑥)
𝑖 𝑡
⇒ 𝐸Ѱ = 𝑖ħმ𝑡Ѱ(𝑥)

Collectively:

( )
2 2 2 2
ħ მ მ მ
Êψ(𝑥, 𝑦, 𝑧, 𝑡) = − 2𝑚
( 2 + 2 + 2 ) + 𝑣(𝑥, 𝑦, 𝑧, 𝑡) ψ(𝑥, 𝑦, 𝑧, 𝑡)
მ𝑥 მ𝑦 მ𝑧
 8

( )
2 2 2 2
მ ħ მ მ მ
⇒ 𝑖ħ მ𝑡
Ѱ(𝑥, 𝑦, 𝑧, 𝑡) = − 2𝑚
( 2 + 2 + 2 ) + 𝑣(𝑥, 𝑦, 𝑧, 𝑡) ψ(𝑥, 𝑦, 𝑧, 𝑡)
მ𝑥 მ𝑦 მ𝑧
2 2 2 2
მ ħ მ მ მ
⇒ 𝑖ħ მ𝑡
Ѱ(𝑥, 𝑦, 𝑧, 𝑡) =− 2𝑚
( 2 ψ(𝑥, 𝑦, 𝑧, 𝑡) + 2 ψ(𝑥, 𝑦, 𝑧, 𝑡) + 2 ψ(𝑥, 𝑦, 𝑧, 𝑡)) + 𝑣(𝑥, 𝑦, 𝑧, 𝑡)ψ(𝑥, 𝑦, 𝑧, 𝑡)
მ𝑥 მ𝑦 მ𝑧

2 2 2 2
მ ħ მ მ მ
𝑖ħ მ𝑡
Ѱ(𝑥, 𝑦, 𝑧, 𝑡) = 𝑣(𝑥, 𝑦, 𝑧, 𝑡)ψ(𝑥, 𝑦, 𝑧, 𝑡) − 2𝑚
( 2 ψ(𝑥, 𝑦, 𝑧, 𝑡) + 2 ψ(𝑥, 𝑦, 𝑧, 𝑡) + 2 ψ(𝑥, 𝑦, 𝑧, 𝑡))
მ𝑥 მ𝑦 მ𝑧

[This is called the “3D” time dependent Schrodinger equation]

Normalization:
Normalization means to introduce a value which computes the wave function in such a way
that its probability to find the particle throughout space-time is ‘1’. By probability, it is
guaranteed to find the particle at any point in space. So, probability density computes the
chances to find the particle in a particular space. Now, we need to define our wave function
as a vector space. So all the regions inside the vector space’s probability need to be one.
Thus, mathematically it is expressed like the following:

∞
⇒ < Ψ *, Ψ > = ∫ Ψ * Ψ 𝑑∆𝑥 ≡ 𝐶
−∞
*
[`Ψ ` means the complex conjugate of our wave function. ]
[Wave function computes a vector space, so a vector space which is complex conjugate, lies opposite of the wave function’s
vector space]
∞
2
⇒ < Ψ *, Ψ > = ∫ |Ψ | 𝑑∆𝑥
−∞
[The modulus means the real component of the wave function]

Proposition:
Ψ2 = 𝑎Ψ
∞
| |2
∫ Ψ2 𝑑∆𝑥 = 1
−∞
∞
2
⇒ < Ψ2 *, Ψ2 > =
−∞
| |
∫ Ψ2 𝑑∆𝑥
∞
2 2
⇒ < Ψ2 *, Ψ2 > = 𝑎 ∫ |Ψ | 𝑑∆𝑥
−∞
2
⇒𝑎 𝐶 = 1
1
⇒𝑎 =
𝐶
[‘a’ is our normalization constant]
 9
∞
2 *
𝑎 ∫ Ψ(∆𝑥, 𝑡)Ψ (∆𝑥, 𝑡)𝑑∆𝑥 𝑑𝑡 = 1
−∞
∞
2 *
⇒ 𝑎 ∫ Ψ(∆𝑥, 𝑡)Ψ (∆𝑥, 𝑡)𝑑∆𝑥 𝑑𝑡 = 1
−∞
∞
2 2
⇒ 𝑎 ∫ |Ψ(∆𝑥, 𝑡)| 𝑑∆𝑥 𝑑𝑡 = 1
−∞
∞
2 2
⇒ 𝑎 ∫ |Ψ(∆𝑥, 𝑡)| 𝑑∆𝑥 𝑑𝑡 = 1
−∞

2
In Volume integration, when transformed to Caartesian, the following change occurs: 𝑑∆𝑥 𝑑𝑡 = 𝑟 𝑠𝑖𝑛θ𝑑θ𝑑ϕ𝑑𝑟𝑑𝑡
∞
2 2 2
⇒ 𝑎 ∫ |Ψ(∆𝑥, 𝑡)| 𝑟 𝑠𝑖𝑛θ𝑑θ𝑑ϕ𝑑𝑟𝑑𝑡 = 1
−∞
∞
2 2 2
⇒ 𝑎 ∫ |𝑇(𝑡)𝑅(𝑟)𝑄(θ)𝐹(ϕ)| 𝑟 𝑠𝑖𝑛θ𝑑θ𝑑ϕ𝑑𝑟𝑑𝑡 = 1
−∞
∞ ∞ ∞ ∞
2 2 2 2 2 2
⇒ 𝑎 ∫ |𝑇(𝑡)| 𝑑𝑡 ∫ |𝑅(𝑟)| 𝑟 𝑑𝑟 ∫ |𝑄(θ)| 𝑠𝑖𝑛θ𝑑θ ∫ |𝐹(ϕ)| 𝑑ϕ = 1
−∞ −∞ −∞ −∞

From the previous line, we can see that our integration can be broken into several
components to make our computation easier. So we will gradually implement the integrations
in our solution.

Schrodinger equation for Hydrogen

Atom:
(also known as: “The Birth of Quantum Numbers”)

Case analysis:
Constituents of Hydrogen Atom is of
the follows:

The picture is for a visual representation. Not to

scale.
This system constitutes an electron
and a proton. They are fermionic
particles, thus they have electric
charge properties. The electron
dissociates from the atom due to
having kinetic energy but cannot
escape due to strong electromagnetic
attraction force. Thus, it’s a single
electron system. The motion of this
system would be purely dependent on
 10
the electron due to overwhelming mass of the proton/(s and electrons). Some atoms can be
hydrogenic. Which means their nucleus may consist of several protons and neutrons but
have only one electron. Due to concentration of the masses and charges at one place, the
whole nucleus is counted as an object/entity at once. This is not only accurate but also
makes our computation efficient. These systems show similar Hydrogen-like properties.
Except for their radius and wavefunction being large, they abstractly show every property of
the Hydrogen atom.

Formulation:
2 2 2 2
მ ħ მ მ მ
𝑖ħ მ𝑡
Ѱ(𝑥, 𝑦, 𝑧, 𝑡) = 𝑣(𝑥, 𝑦, 𝑧, 𝑡)Ѱ(𝑥, 𝑦, 𝑧, 𝑡) − 2𝑚
( 2 Ѱ(𝑥, 𝑦, 𝑧, 𝑡) + 2 Ѱ(𝑥, 𝑦, 𝑧, 𝑡) + 2 Ѱ(𝑥, 𝑦, 𝑧, 𝑡))
მ𝑥 მ𝑦 მ𝑧
2
მ ħ 2
⇒ 𝑖ħ მ𝑡
Ѱ = 𝑣Ѱ − 2𝑚
(∇ Ѱ)

Proposition:
Ѱ(𝑥, 𝑦, 𝑧, 𝑡) = 𝑇(𝑡)ψ(𝑥, 𝑦, 𝑧)

Continuation:
2
მ ħ 2
𝑖ħ მ𝑡
Ѱ = 𝑣Ѱ − 2𝑚
(∇ Ѱ)
2
მ ħ 2
⇒ 𝑖ħ მ𝑡
[𝑇(𝑡)ψ(𝑥, 𝑦, 𝑧)] = 𝑣𝑇(𝑡)ψ(𝑥, 𝑦, 𝑧) − 2𝑚
(∇ 𝑇(𝑡)ψ(𝑥, 𝑦, 𝑧))
2
მ ħ 2
⇒ 𝑖ħ მ𝑡
[𝑇ψ] = 𝑣𝑇ψ − 2𝑚
(∇ 𝑇ψ)
2
მ ħ 2
⇒ 𝑖ħψ მ𝑡
[𝑇] = 𝑣𝑇ψ − 𝑇 2𝑚
(∇ ψ)
2
მ ħ 2
𝑖ħψ მ𝑡 [𝑇] 𝑣𝑇ψ−𝑇 2𝑚 (∇ ψ)
⇒ 𝑇ψ
= 𝑇ψ
[Divide both sides by ‘𝑇ψ’]
2
მ ħ 2
𝑖ħ მ𝑡 [𝑇] 2𝑚
(∇ ψ)
⇒ 𝑇
=𝑣− ψ

Separation of Time-space components:

Both sides of our equation have been separated. Now. we will set both sides equal to a
constant namely ‘E’.

მ
𝑖ħ მ𝑡 [𝑇]
𝑇
=𝐸
2
ħ 2
2𝑚
(∇ ψ)
𝐸=𝑣− ψ

Time component solution:

მ
𝑖ħ მ𝑡 [𝑇]
𝑇
=𝐸
 11
მ𝑇 𝐸მ𝑡
⇒ 𝑇
= 𝑖ħ
მ𝑇 𝐸მ𝑡
⇒ 𝑇
=− 𝑖 ħ

მ𝑇 𝐸
⇒∫ 𝑇
=− 𝑖 ħ
∫ მ𝑡
𝐸
⇒ 𝑙𝑛|𝑇| =− 𝑖 ħ
𝑡 + 𝑡0
𝐸
−𝑖 ħ 𝑡+𝑡0
⇒𝑇 =𝑒
𝐸
−𝑖 ħ 𝑡
⇒ 𝑇 = 𝑡1𝑒

Spatial component solution:

2
ħ 2
2𝑚
(∇ ψ)
𝐸=𝑣− ψ

( )
2
ħ 2
2𝑚
(∇ ψ)
⇒𝐸 × ψ = 𝑣 − ψ
× ψ
[Multiply both sides by ‘ψ’]
2
ħ 2
⇒ 𝐸ψ = 𝑣ψ − 2𝑚
(∇ ψ)
2
ħ 2
⇒ ψ(𝐸 − 𝑣) =− 2𝑚
(∇ ψ)
2𝑚 2
⇒ 2 ψ(𝐸 − 𝑣) =− ∇ ψ
ħ
2𝑚 2
⇒ 2 ψ(𝐸 − 𝑣) + ∇ ψ = 0
ħ
[General form][Also in your book]
In an Hydrogen atom, the mass we will consider the center mass of both the proton and the electron. So, mass would be: µ
𝑚𝑝𝑚𝑒
µ= 𝑚𝑝+𝑚𝑒

[`𝑚𝑒` is electron mass and ‘𝑚𝑝` is proton mass]

Explanation for coordinate transformation

2
𝑒
Also, the potential energy of the atom would be the energy from electromagnetic force. So, 𝑣 =− 4πε0𝑟

But here, we can see that the potential energy is a function of radius, but our schrodinger’s equation is in x,y, z axis
coordinates.
2
2𝑚 𝑒 2
⇒ 2 ψ(𝐸 + 4πε0𝑟
) +∇ ψ = 0
ħ
2
2𝑚 𝑒 2
⇒ 2 ψ(𝐸 + 2 2 2
) +∇ ψ = 0
ħ 4πε0 𝑥 +𝑦 +𝑧
2 2 2 2
[𝑟 = 𝑥 + 𝑦 + 𝑧 ]
2
𝑚 𝑒 2 2𝑚
⇒ 2 2 2 2
ψ =− (∇ ψ + 2 𝐸ψ)
ħ 2πε0 𝑥 +𝑦 +𝑧 ħ

2
⎡𝑚 2 ⎤ 2
2
ψ⎥ = ⎡⎢− (∇ ψ + 𝐸ψ)⎤⎥
𝑒 2𝑚
⇒⎢ 2 2
⎢ħ 2πε0 𝑥 +𝑦 +𝑧
2 2 2 ⎥ ⎣ ħ ⎦
⎣ ⎦
2 4
𝑚 𝑒 2 2 2𝑚 2
⇒ 4 2 2 2 2 2 |ψ| = (∇ ψ + 2 𝐸ψ)
ħ 4π ε0 (𝑥 +𝑦 +𝑧 ) ħ
 12
2 4
𝑚 𝑒 2 2 2 2 2𝑚 2𝑚 2
⇒ 4 2 2 2 2 2 |ψ| = (∇ ψ) + 2(∇ ψ)( 2 𝐸ψ) + ( 2 𝐸ψ)
ħ 4π ε0 (𝑥 +𝑦 +𝑧 ) ħ ħ
2 4
𝑚 𝑒 2 2 2 4𝑚 2 2𝑚 2 2
⇒ 4 2 2 2 2 2 |ψ| = (∇ ψ) + 2 (∇ ψ)(𝐸ψ)𝑐𝑜𝑠α + ( 2 𝐸) |ψ|
ħ 4π ε0 (𝑥 +𝑦 +𝑧 ) ħ ħ
What’s worse is that the last line equation is inseparable by every means. Not only is it inseparable, now it has an additional
alpha term within it due to dot product rule. So it would be a straight dead end for our formulation if we choose to stick to our
cartesian coordinates to obtain our solution for the Schrodinger's wave equation.

So it would be very troublesome to calculate in this way, thus we have to convert our Laplacian into spherical coordinates.

2
2 1 ∂ 2 ∂ψ 1 ∂ ∂ψ 1 ∂ψ
∇ψ= 2 ∂𝑟
(𝑟 ∂𝑟
)+ 2 (𝑠𝑖𝑛θ )+ 2 2 2
𝑟 𝑟 𝑠𝑖𝑛θ ∂θ ∂θ 𝑟 𝑠𝑖𝑛 θ ∂ ϕ

The derivation of transforming Cartesian Laplacian into spherical coordinates is given:

Laplacian coordinate transformation

So, the schrodinger’s equation for our hydrogen atom looks like this:
2
2𝑚 𝑒 2
2 ψ(𝐸 + 4πε0𝑟
) +∇ ψ = 0
ħ
2
2µ 1 ∂ 2 ∂ψ 1 ∂ ∂ψ 1 ∂ψ
⇒ 2 Ѱ(𝐸 − 𝑣) + [ 2 ∂𝑟
(𝑟 ∂𝑟
)+ 2 (𝑠𝑖𝑛θ )+ 2 2 2 ]=0
ħ 𝑟 𝑟 𝑠𝑖𝑛θ ∂θ ∂θ 𝑟 𝑠𝑖𝑛 θ ∂ ϕ

Separation of Radial and angular components:

Now, we will perform the separation of variables method in order to solve this 2nd order
partial differential equation.

Ѱ(𝑟, θ, ϕ) = 𝑅(𝑟)𝑌(θ, ϕ)

Computation table:

∂ ∂
∂𝑟
Ѱ= ∂𝑟
(𝑅𝑌)
∂ ∂
⇒ ∂𝑟
Ѱ=𝑌 ∂𝑟
(𝑅)

∂ ∂
∂θ
Ѱ= ∂θ
(𝑅𝑌)
∂ ∂
⇒ ∂θ
Ѱ=𝑅 ∂θ
(𝑌)

∂ ∂
∂ϕ
Ѱ= ∂ϕ
(𝑅𝑌)
∂ ∂
⇒ ∂ϕ
Ѱ=𝑅 ∂ϕ
(𝑌)
∂ ∂ ∂ ∂
⇒ ∂ϕ
( ∂ϕ Ѱ) = ∂ϕ
[𝑅 ∂ϕ
(𝑌)]
2 2
∂ ∂
⇒ 2 Ѱ=𝑅 2 𝑌
∂ϕ ∂ϕ
 13

Continuation:
Now, put these values we obtained from the computation table into our schrodinger
equation:

2
2µ 1 ∂ 2 ∂ 1 ∂ ∂ 1 ∂
2 𝑅𝑌(𝐸 − 𝑣) + [ 2 ∂𝑟
(𝑟 𝑌 ∂𝑟
(𝑅)) + 2 (𝑠𝑖𝑛θ𝑅 (𝑌)) + 2 2 𝑅 2 𝑌] = 0
ħ 𝑟 𝑟 𝑠𝑖𝑛θ ∂θ ∂θ 𝑟 𝑠𝑖𝑛 θ ∂ϕ
2
2µ 𝑌 ∂ 2 ∂ 𝑅∂ ∂ 𝑅 ∂
⇒ 2 𝑅𝑌(𝐸 − 𝑣) + [ 2 ∂𝑟
(𝑟 ∂𝑟
(𝑅)) + 2 ∂θ
(𝑠𝑖𝑛θ ∂θ
(𝑌)) + 2 2 2 𝑌] = 0
ħ 𝑟 𝑟 𝑠𝑖𝑛θ 𝑟 𝑠𝑖𝑛 θ ∂ϕ
2 2 2
𝑟 2µ 𝑌 ∂ 2 ∂ 𝑅 ∂ ∂ 𝑅 ∂ 𝑟
⇒ 𝑅𝑌
×[ 2 𝑅𝑌(𝐸 − 𝑣) + [ 2 ∂𝑟
(𝑟 ∂𝑟
(𝑅)) + 2 (𝑠𝑖𝑛θ (𝑌)) + 2 2 2 𝑌]] = ×0
ħ 𝑟 𝑟 𝑠𝑖𝑛θ ∂θ ∂θ 𝑟 𝑠𝑖𝑛 θ ∂ϕ 𝑅𝑌
2
2µ 2 1 ∂ 2 ∂ 1 ∂ ∂ 1 ∂
⇒ 2 𝑟 (𝐸 − 𝑣) + [ 𝑅 ∂𝑟
(𝑟 ∂𝑟
(𝑅)) + 𝑌𝑠𝑖𝑛θ ∂θ
(𝑠𝑖𝑛θ ∂θ
(𝑌)) + 2 2 𝑌] = 0
ħ 𝑌𝑠𝑖𝑛 θ ∂ϕ
2
2µ 2 1 ∂ 2 ∂ 1 1 ∂ ∂ 1 ∂
⇒ 2 𝑟 (𝐸 − 𝑣) + 𝑅 ∂𝑟
(𝑟 ∂𝑟
(𝑅)) =− 𝑌
[ 𝑠𝑖𝑛θ ∂θ
(𝑠𝑖𝑛θ ∂θ
(𝑌)) + 2 2 𝑌]
ħ 𝑠𝑖𝑛 θ ∂ϕ

If we notice, the left hand side only contains components with respect to ‘R’ and the right
hand side contains components with respect to ‘Y’. So, to solve them, we will set each of the
sides to a constant namely ‘A’.

2µ 2 1 ∂ 2 ∂
2 𝑟 (𝐸 − 𝑣) + 𝑅 ∂𝑟
(𝑟 ∂𝑟
(𝑅)) = 𝐴 [This is called radial equation]
ħ
2
1 1 ∂ ∂ 1 ∂
− 𝑌
[ 𝑠𝑖𝑛θ ∂θ
(𝑠𝑖𝑛θ ∂θ
(𝑌)) + 2 2 𝑌] = 𝐴 [This is called Angular equation]
𝑠𝑖𝑛 θ ∂ϕ

If we recall, our ∀𝑌¬(θ, ϕ). Thus, ‘Y’ function can be further separated into functions which
will have ‘θ, ϕ’ in them only respectively.

Separation of Polar and Angular equations:

Proposition:
𝑌(θ, ϕ) = 𝑄(θ)𝐹(ϕ)

Computation Table
∂ ∂
⇒ ∂θ
𝑌=𝐹 ∂θ
𝑄

𝑌(θ, ϕ) = 𝑄(θ)𝐹(ϕ)
∂ ∂
⇒ ∂ϕ
𝑌=𝑄 ∂ϕ
𝐹
2 2
∂ ∂
⇒ 2 𝑌=𝑄 2 𝐹
∂ϕ ∂ϕ

Continuation
2
1 1 ∂ ∂ 1 ∂
− 𝑌
[ 𝑠𝑖𝑛θ ∂θ
(𝑠𝑖𝑛θ ∂θ
(𝑌)) + 2 2 𝑌] = 𝐴
𝑠𝑖𝑛 θ ∂ϕ
 14
2
1 1 ∂ ∂ 𝑄 ∂
⇒− 𝑄𝐹
[ 𝑠𝑖𝑛θ ∂θ
(𝐹𝑠𝑖𝑛θ ∂θ
𝑄) + 2 2 𝐹] = 𝐴
𝑠𝑖𝑛 θ ∂ϕ
2
1 1 ∂ ∂ 1 1 ∂
⇒− 𝑄 𝑠𝑖𝑛θ ∂θ
(𝑠𝑖𝑛θ ∂θ
𝑄) = 𝐴 + 𝐹 𝑠𝑖𝑛2θ ∂ϕ2
𝐹
2
1 1 ∂ ∂ 1 1 ∂
⇒ 𝑄 𝑠𝑖𝑛θ ∂θ
(𝑠𝑖𝑛θ ∂θ
𝑄) + 𝐴 = − 𝐹 𝑠𝑖𝑛2θ ∂ϕ2
𝐹
2
𝑠𝑖𝑛θ ∂ ∂ 2 1 ∂
⇒ 𝑄 ∂θ
(𝑠𝑖𝑛θ ∂θ
𝑄) + 𝐴𝑠𝑖𝑛 θ = − 𝐹 ∂ϕ2
𝐹

Polar and angular equations

If we notice, the left hand side only contains components with respect to ‘Q’ and the right
hand side contains components with respect to ‘F’. So, to solve them, we will set each of the
sides to a constant namely ‘B’.

𝑠𝑖𝑛θ ∂ ∂ 2
1. 𝑄 ∂θ
(𝑠𝑖𝑛θ ∂θ
𝑄) + 𝐴𝑠𝑖𝑛 θ = 𝐵 [This is called polar equation]
2
1 ∂
2. − 𝐹 ∂ϕ2
𝐹=𝐵 [This is called Azimuthal/subsidiary
quantum equation]

Azimuthal equation
2
1 ∂
− 𝐹 ∂ϕ2
𝐹=𝐵
2
∂
⇒ 2 𝐹= − 𝐵𝐹
∂ϕ
2
⇒ 𝐷 𝐹 + 𝐵𝐹 = 0 [Here, ‘D’ is the differential operator with respect to ‘ϕ’]
2
⇒ 𝐹(𝐷 + 𝐵) = 0
2
⇒𝐷 + 𝐵 = 0
⇒ 𝐷 =± 𝐵𝑖
𝑑
⇒ 𝑑ϕ
=± 𝐵𝑖
𝑑𝐹
⇒ 𝑑ϕ
=± 𝐹 𝐵𝑖
𝑑𝐹
⇒ 𝐹
= (± 𝐵𝑖)𝑑ϕ

𝑑𝐹
⇒∫ 𝐹
= ∫(± 𝐵𝑖)𝑑ϕ

𝑑𝐹
⇒∫ 𝐹
= (± 𝐵𝑖) ∫ 𝑑ϕ

⇒ 𝑙𝑛(𝐹) =± ϕ 𝐵𝑖 + 𝑘 [‘k’ here is an integration arbitrary constant]

𝑙𝑛(𝐹) ±ϕ 𝐵𝑖+𝑘
⇒𝑒 =𝑒
±ϕ 𝐵𝑖
⇒ 𝐹 = 𝑘𝑒

Therefore, both solutions of F satisfy the given differential equation. That implies any linear combination of the above two
solutions satisfies the differential equation. Therefore, the final solution would be:
 15
ϕ 𝐵𝑖 −ϕ 𝐵𝑖
𝐹 = 𝑘1𝑒 + 𝑘2𝑒

Solution analysis
−ϕ 𝐵𝑖
In physical context, 𝐹2 = lim 𝑘2𝑒 = 0 and thus `𝐹2` is a redundant solution. Also, our
ϕ→∞
‘B’ constant is now operating under a square root, which is essentially 𝐵: 𝑍 → ¬(𝑁 ∧ 𝑍). In
order to make 𝐵: 𝑍 → 𝑁, we need to set it to some other constant, which we name as:
2 1
𝐵 = 𝑚 . Also, ‘k’ will be set as our normalization constant. Thus, 𝑘 = ∫|𝐹 * 𝐹|𝑑ϕ = 2π

ϕ 𝐵𝑖
𝑒
𝐹= 2π

If we notice the above function, ‘F’, then we can see that it follows the euler identity:

𝐹(Φ) = 𝐹(Φ + 2π)

ϕ 𝐵𝑖 (Φ+2π) 𝐵𝑖
𝑒 𝑒
⇒ 2π
= 2π
2π 𝐵𝑖
⇒𝑒 =1
⇒ 𝑐𝑜𝑠(2π 𝐵) + 𝑖𝑠𝑖𝑛(2π 𝐵) = 1
⇒ 𝑐𝑜𝑠(2π 𝐵) = 1

Now, ( 𝑐𝑜𝑠(𝑥) ⇔ 1: 𝑥 ∈ 2π(𝑁 ∧ {0}) ). This implies that, 𝑐𝑜𝑠(𝑥) will be equal to one iff ‘x’ is
an multiple of ‘2π` even including the zeroth multiple. In our expression, we only have one
variable constant operating under a square root. So essentially we need to introduce a new
constant such that when we will input value, it will preserve the above identity. So, let:
𝐵= 𝑚
2
⇒𝐵 =𝑚

But we know, a squared number also holds this identity: 𝑚: 𝑍 → 𝑁. So, we can include all the
range of integer numbers into our ‘m’ and by doing such, we can say the following: 𝑚 ⊆ 𝑍

Magnetic quantum number

𝑚 = 0, ± 1, ± 2, ± 3, ± 4,....

Polar equation:
𝑠𝑖𝑛θ ∂ ∂ 2
𝑄 ∂θ
(𝑠𝑖𝑛θ ∂θ
𝑄) + 𝐴𝑠𝑖𝑛 θ = 𝐵
𝑠𝑖𝑛θ ∂ ∂ 2 2
⇒ 𝑄 ∂θ
(𝑠𝑖𝑛θ ∂θ
𝑄) + 𝐴𝑠𝑖𝑛 θ = 𝑚
𝑠𝑖𝑛θ ∂ ∂ 2 2
⇒ 𝑄 ∂θ
(𝑠𝑖𝑛θ ∂θ
𝑄) + (𝐴𝑠𝑖𝑛 θ − 𝑚 ) = 0
∂ ∂ 2 2
⇒ 𝑠𝑖𝑛θ ∂θ
(𝑠𝑖𝑛θ ∂θ
𝑄) + (𝐴𝑠𝑖𝑛 θ − 𝑚 )𝑄 = 0
 16
2
1 ∂ ∂ 𝑚
⇒ 𝑠𝑖𝑛θ ∂θ
(𝑠𝑖𝑛θ ∂θ
𝑄) + (𝐴 − 2 )𝑄 = 0
𝑠𝑖𝑛 θ

Proposition:
𝑃(𝑐𝑜𝑠θ) = 𝑄(θ)
𝑗 = 𝑐𝑜𝑠θ
𝑑𝑗
⇒ 𝑑θ
= − 𝑠𝑖𝑛θ
∂𝑗 ∂ ∂
⇒ ∂θ ∂𝑗
=− 𝑠𝑖𝑛θ ∂𝑗

2
1 ∂ ∂ 𝑚
𝑠𝑖𝑛θ ∂θ
(𝑠𝑖𝑛θ ∂θ
𝑄) + (𝐴 − 2 )𝑄 = 0
𝑠𝑖𝑛 θ
2
1 ∂ ∂ 𝑚
⇒ 𝑠𝑖𝑛θ
[− 𝑠𝑖𝑛θ ∂𝑗
(𝑠𝑖𝑛θ(− 𝑠𝑖𝑛θ ∂𝑗
𝑃)] + (𝐴 − 2 )𝑃 = 0
𝑠𝑖𝑛 θ
2
∂ 2 ∂ 𝑚
⇒ ∂𝑗
(𝑠𝑖𝑛 θ( ∂𝑗 𝑃) + (𝐴 − 2 )𝑃 = 0
𝑠𝑖𝑛 θ
2
∂ 2 ∂ 𝑚 2 2
⇒ ∂𝑗
[(1 − 𝑐𝑜𝑠 θ) ∂𝑗
𝑃] + (𝐴 − 2 )𝑃 = 0 [𝑠𝑖𝑛 θ = 1 − 𝑐𝑜𝑠 θ]
1−𝑐𝑜𝑠 θ
2 2
2 ∂ ∂𝑃 𝑚
⇒ (1 − 𝑗 ) 2 𝑃 − 2𝑗 ∂𝑗
+ (𝐴 − 2 )𝑃 = 0
∂𝑗 1−𝑗

Now, if we notice that the above equation can be bought into the “Associative Legendre’s
differential equation” if we let `𝐴 = 𝑙(𝑙 + 1)`

2 2
2 ∂ ∂𝑃 𝑚
(1 − 𝑗 ) 2 𝑃 − 2𝑗 ∂𝑗
+ (𝑙(𝑙 + 1) − 2 )𝑃 = 0
∂𝑗 1−𝑗

The workings for obtaining the solution is given here:

Associated Legendre's differential equation

Thus, from the document given above, we can tell that the solution for that differential
equation is:

Azimuthal, Subsidiary/subshell quantum number condition:

[𝑙 ≥ |𝑚|]

Continuation
𝑚
⎡(1 − 𝑗2) 2
⇒ 𝑃(𝑗) =
2𝑙+1 (𝑙−𝑚)!
2 (𝑙+𝑚)! ⎢
⎣
1
𝑙
2 𝑙!
𝐷
𝑙+𝑚
[(− 1)𝑙(1 − 𝑗2)𝑙]⎤⎥⎦
|𝑚|
𝑙 2 𝑙+|𝑚|
⇒ 𝑃(𝑐𝑜𝑠θ) =
2𝑙+1 (𝑙−|𝑚|)!
2 (𝑙+|𝑚|)!
(− 1) (𝑠𝑖𝑛 θ) 2 1
𝑙
2 𝑙!
𝐷 [(𝑠𝑖𝑛2θ)𝑙]
𝑙 |𝑚| 1 𝑙+|𝑚|
⇒ 𝑄(θ) =
2𝑙+1 (𝑙−|𝑚|)!
2 (𝑙+|𝑚|)!
(− 1) (𝑠𝑖𝑛θ)
2 𝑙!
𝑙 𝐷 [(𝑠𝑖𝑛θ)2𝑙]
 17

Radial equation:
2µ 2 1 ∂ 2 ∂
2 𝑟 (𝐸 − 𝑣) + 𝑅 ∂𝑟
(𝑟 ∂𝑟
(𝑅)) = 𝐴
ħ
2 2
2µ 2 𝑒 ∂ 2 ∂
⇒ 2 𝑟 𝑅(𝐸 − (− 4πε0𝑟
)) + 2 (𝑅) + 𝑟 ∂𝑟
(𝑅) = 𝑙(𝑙 + 1)𝑅
ħ ∂𝑟
2 2
2µ 2µ 𝑒 𝑙(𝑙+1) ∂ 2 ∂
⇒ 𝑅( 2 𝐸+ 2 4πε0𝑟
− 2 )+ 2 (𝑅) + 𝑟 ∂𝑟
(𝑅) = 0
ħ ħ 𝑟 ∂𝑟

Case:1
At, 𝑟 → ∞

2 2
2µ 2µ 𝑒 𝑙(𝑙+1) ∂ 2 ∂
lim ⇒ 𝑅( 2 𝐸+ 2 4πε0𝑟
− 2 )+ 2 (𝑅) + 𝑟 ∂𝑟
(𝑅) = lim 0
𝑟→∞ ħ ħ 𝑟 ∂𝑟 𝑟→∞
2
2µ ∂
⇒ 2 𝑅(𝐸) + 2 (𝑅) = 0
ħ ∂𝑟
2
2µ𝐸 ∂
⇒ 2 𝑅+ 2 (𝑅) = 0
ħ ∂𝑟
1 1
− 2 𝑘𝑟 𝑘𝑟 8µ𝐸
⇒ 𝑅 = 𝐴𝑒 + 𝐵𝑒 2 [κ = − 2 ]
ħ

In this case, the function will have to diverge at infinity. Thus, `𝐵 = 0`

1
− 2 𝑘𝑟
⇒ 𝑅 = 𝐴𝑒

Case:2
At, 𝑟 → 0

2 2
2µ 2µ 𝑒 𝑙(𝑙+1) ∂ 2 ∂
lim ⇒ 𝑅( 2 𝐸+ 2 4πε0𝑟
− 2 )+ 2 (𝑅) + 𝑟 ∂𝑟
(𝑅) = lim 0
𝑟→0 ħ ħ 𝑟 ∂𝑟 𝑟→0
2
∂ 2 ∂ 𝑙(𝑙+1)
⇒ 2 (𝑅) + 𝑟 ∂𝑟
(𝑅) − 𝑅( 2 )=0
∂𝑟 𝑟

You can notice a polynomial differentiation pattern emerging, thus we can do the following
α
assumption: 𝑅 = 𝑟

2
∂ 2 ∂ 𝑙(𝑙+1)
2 (𝑅) + 𝑟 ∂𝑟
(𝑅) − 𝑅( 2 )=0
∂𝑟 𝑟
2
∂ α 2 ∂ α α 𝑙(𝑙+1)
⇒ 2 (𝑟 ) + 𝑟 ∂𝑟
(𝑟 ) − (𝑟 )( 2 )=0
∂𝑟 𝑟
α α−2 α−2
⇒ α(α − 1)(𝑟 ) + 2(α𝑟 ) − (𝑟 )𝑙(𝑙 + 1) = 0
α−2
⇒ [α(α + 1) − 𝑙(𝑙 + 1)]𝑟 =0

α = 𝑙, − (𝑙 + 1)
 18

Case:3
At the continuity,

Proposition:
2 8𝑚𝐸
κ = − 2
ћ
κ𝑟 = 𝑥
2
2µ 𝑒
λ= 2 4πε0
ħ
 19

Overall:
The method of solving Laguerre differential equation is given in the following:

Associated Laguerre Differential Equation

Normalization of radial term:

2𝑙+1
Thus, 𝑍 = 𝑁2𝑙+1, λ−𝑙−1𝐿 λ−𝑙−1
2𝑙+1
⇒ 𝑍 = 𝑁2𝑙+1, λ−𝑙−1𝐿 λ−𝑙−1
𝑥
2 −𝑙 2𝑙+1
⇒ ψ𝑒 𝑥 = 𝑁2𝑙+1, λ−𝑙−1𝐿 λ−𝑙−1
𝑥
2𝑙+1 −2 𝑙
⇒ ψ = 𝑁2𝑙+1, λ−𝑙−1𝐿 λ−𝑙−1
(𝑥)𝑒 𝑥

Here,

1
𝑁2𝑙+1, λ−𝑙−1 =
∞
−3 −𝑥 2𝑙+1 2𝑙+1 2
κ ∫𝑒 𝑥 [𝐿 λ−𝑙−1
] 𝑑𝑥
0

3 (λ−𝑙−1)!
⇒ 𝑁2𝑙+1, λ−𝑙−1 = κ 3
2λ(λ+1)!
 20

Energy quantisation:
After doing a “Power series solution” to the Laguerre differential equation, you will be
familiarize with the following term:
 21

2 2
𝑍𝑒
𝐸𝑛 =− 2 [In SI. system]
8πε0𝑎0𝑛

Wave equation for hydrogen:

As we declared our wave equation to be in the following format:
Ѱ(𝑥, 𝑦, 𝑧, 𝑡) = 𝑇(𝑡)ψ(𝑥, 𝑦, 𝑧)
⇒ Ѱ(𝑥, 𝑦, 𝑧, 𝑡) = 𝑇(𝑡)𝑅(𝑟)𝑌(θ, ϕ)
⇒ Ѱ(𝑥, 𝑦, 𝑧, 𝑡) = 𝑇(𝑡)𝑅(𝑟)𝑄(θ)𝐹(ϕ)
ρ
3 (λ−𝑙−1)! 2𝑙+1 −2 𝑙
⇒ψ = κ 3 𝐿 λ−𝑙−1
(ρ)𝑒 ρ
2λ(λ+1)!
8µ𝐸
3 − 2
𝑟 𝑙
ħ
8µ𝐸 (λ−𝑙−1)! 2𝑙+1 8µ𝐸 − 2 8µ𝐸
⇒ψ = ( − 2 ) 3 𝐿 λ−𝑙−1
( − 2 𝑟)𝑒 ( − 2 𝑟)
ħ 2λ(λ+1)! ħ ħ
8µ𝐸
3 − 2
𝑟 𝑙
𝐸 − ħ ϕ 𝐵𝑖
−𝑖 ħ 𝑡 2𝑙+1 𝑙 |𝑚| 1 𝑙+|𝑚|
⇒ Ѱ(𝑥, 𝑦, 𝑧, 𝑡) = 𝑡1𝑒 ( −
8µ𝐸
2
ħ
)
(λ−𝑙−1)!
2λ(λ+1)!
3 𝐿
λ−𝑙−1
( −
8µ𝐸
ħ
2 𝑟)𝑒 2
( −
8µ𝐸
ħ
2 𝑟)
2𝑙+1 (𝑙−|𝑚|)!
2 (𝑙+|𝑚|)!
(− 1) (𝑠𝑖𝑛θ) 𝑙
2 𝑙!
𝐷 [(𝑠𝑖𝑛θ)2𝑙] 𝑒2π
𝑟
3 (𝑛−𝑙−1)! −𝑖𝑛𝑅𝐻𝑐𝑡 2𝑙+1 − 𝑛𝑎 𝑙 𝑙 |𝑚| 1 𝑙+|𝑚|
⇒ Ѱ𝑛,𝑙,𝑚(𝑥, 𝑦, 𝑧, 𝑡) = 𝑡1
2
( 𝑛𝑎 )
0 2𝑛(𝑛+1)!
3
2𝑙+1 (𝑙−|𝑚|)!
8π
2 (𝑙+|𝑚|)!
𝑒 𝐿 ⎡ 2𝑟
𝑛−𝑙−1⎢ 𝑛𝑎0
⎣
⎤𝑒
⎥
⎦
0 2𝑟
( 𝑛𝑎 ) (− 1) (𝑠𝑖𝑛θ)
0
𝑙
2 𝑙!
𝐷 [(𝑠𝑖𝑛θ)2𝑙]𝑒ϕ|𝑚|𝑖
 22

Schrodinger Equation for Helium and

multi-electron systems:
(The birth of approximate methods)

Case analysis:

The picture is for a visual representation. Not to scale.

This system constitutes two electrons and 2 protons and 2 neutrons. They are fermionic
particles, thus protons and electrons have electric charge properties. The electrons
dissociate from the atom due to having kinetic energy but cannot escape due to strong
electromagnetic attraction force. Also electromagnetic force is a field force, so each
electron’s electromagnetic force affects the other electrons too. Thus in this system, an
 23
electron-electron repulsion force is acting on it unlike hydrogenic systems. Thus, it’s a
multi-electron system. The motion of this system would be purely dependent on the electron
due to overwhelming mass of the proton/(s and electrons). Some atoms can be Helium-like.
Which means their nucleus may consist of several protons and neutrons but have only one
electron. Due to concentration of the masses and charges at one place, the whole nucleus is
counted as an object/entity at once. This is not only accurate but also makes our
computation efficient. These systems show similar Hydrogen-like properties. Except for their
radius and wavefunction being large, they abstractly show every property of the Hydrogen
atom.

Formulation:
2
მ ħ 2
𝑖ħ მ𝑡
Ѱ = 𝑣Ѱ − 2𝑚
(∇ Ѱ)
2
მ 𝑍𝑒
2
𝑍𝑒
2 𝑍2𝑒 ħ
2
2 2 ħ
2
⇒ 𝑖ħ მ𝑡
Ѱ=( 4πε0𝑟1
+ 4πε0𝑟2
− 4πε0𝑟12
)Ѱ − 2𝑚
(∇1 + ∇2 )Ѱ − 2𝑀
(∇1 · ∇2)Ѱ
[Implementation of the schrodinger’s equation for Helium system]
2 2
მ 2𝑒 1 1 1 ħ 2 2
⇒ 𝑖ħ მ𝑡
Ѱ= 4πε0
( 𝑟1
+ 𝑟2
− 2𝑟12
)Ѱ − 2𝑚
(∇1 + ∇2 )Ѱ
[The mass of the Nucleus is considered too much, ‘M’ is very large and thus it’s reciprocal becomes negligible ]
[In this case, ‘𝑍 = 2,𝑍2 = 1’]
2 2
მ 𝑒 1 1 1 ħ 2 2
⇒ 𝑖ħ მ𝑡
Ѱ= 2πε0
(𝑟 + 𝑟2
− 2𝑟12
)Ѱ − 2𝑚
(∇1 + ∇2 )Ѱ
1

Explanation of unsolvability:
1
Now, the issue is that the above term is inseparable due to the presence of the term: ` 2𝑟 `
12

So, we cannot solve this Partial differential equation analytically. Under such circumstances,
various approximation methods need to be introduced.

Famous approximation methods:

1. Variational method
2. Perturbation theory
3. Hartree-Fock method
4. LCAO method

This list is exhaustible. So several newer and more sophisticated methods may be
discovered for approximating an Atom’s energy states with the pinpoint accuracy close to the
experimental data.

This is true for all ‘n-body’ problems. So a system with ‘n’ electrons schrodinger is derived
from the observation above:
 24

N-electron system schrodinger equation

2 𝑛 2 𝑛 2
მ 2
Ѱ ∑ ⎡⎢ 𝑟 ⎤⎥ − ∑⎡⎢ 𝑟 ⎤⎥
𝑍𝑒 1 ħ 𝑒 1
𝑖ħ მ𝑡
Ѱ= 4πε0 2𝑚
∑ ⎡⎢∇𝑖 Ѱ⎤⎥ − 4πε0
𝑖=1⎣ 𝑖 ⎦ 𝑖=1⎣ ⎦ 𝑖,𝑗 ⎣ 𝑖𝑗 ⎦

Computation of ground state of Helium

Formulation
2 𝑛 2 𝑛 2
მ 2
Ѱ ∑ ⎡⎢ 𝑟 ⎤⎥ − ∑⎡⎢ 𝑟 ⎤⎥
𝑍𝑒 1 ħ 𝑒 1
𝑖ħ მ𝑡
Ѱ= 4πε0 2𝑚
∑ ⎡⎢∇𝑖 Ѱ⎤⎥ − 4πε0
𝑖=1⎣ 𝑖 ⎦ 𝑖=1 ⎣ ⎦ 𝑖,𝑗 ⎣ 𝑖𝑗 ⎦
2 2 2 2
მ 2
Ѱ ∑ ⎡⎢ 𝑟 ⎤⎥ −
2𝑒 1 ħ
⇒ 𝑖ħ მ𝑡
Ѱ= 4πε0 2𝑚
∑ ⎡⎢∇𝑖 Ѱ⎤⎥
𝑖=1 𝑖 ⎦
⎣ 𝑖=1⎣ ⎦
2 2
მ 𝑒 1 1 ħ 2 2
⇒ 𝑖ħ მ𝑡
Ѱ= 2πε0
(𝑟 + 𝑟2
)Ѱ − 2𝑚
(∇1 + ∇2 )Ѱ
1
2 2 2 2
მ 𝑒 1 ħ 2 𝑒 1 ħ 2
⇒ 𝑖ħ მ𝑡
Ѱ= 2πε0 𝑟1
Ѱ− 2𝑚
∇1 Ѱ + 2πε0 𝑟2
Ѱ− 2𝑚
∇2 Ѱ
2 2 2 2
𝑒 1 ħ 2 𝑒 1 ħ 2
⇒ 𝐸Ѱ = 2πε0 𝑟1
Ѱ− 2𝑚
∇1 Ѱ + 2πε0 𝑟2
Ѱ− 2𝑚
∇2 Ѱ

Proposition:
100 100
Ѱ =𝑈 1
(𝑟1)𝑈 2
(𝑟2)
⇒ Ѱ = 𝑈1𝑈2
2 2 2 2
𝑒 1 ħ 2 𝑒 1 ħ 2
𝐸Ѱ = 2πε0 𝑟1
Ѱ− 2𝑚
∇1 Ѱ + 2πε0 𝑟2
Ѱ− 2𝑚
∇2 Ѱ
2 2 2 2
𝑒 1 ħ 2 𝑒 1 ħ 2
⇒ 𝐸𝑈1𝑈2 = 2πε0 𝑟1
𝑈1𝑈2 − 2𝑚
∇1 𝑈1𝑈2 + 2πε0 𝑟2
𝑈1𝑈2 − 2𝑚
∇2 𝑈1𝑈2
2 2 2 2
𝑒 1 ħ 2 𝑒 1 ħ 2
⇒𝐸 = 2πε0 𝑟1
− 2𝑚𝑈1
∇1 𝑈1 + 2πε0 𝑟2
− 2𝑚𝑈2
∇2 𝑈2

Proposition:
𝐸=𝐴+𝐵
2 2
𝑒 1 ħ 2
𝐴= 2πε0 𝑟1
− 2𝑚𝑈1
∇1 𝑈1
2 2
𝑒 1 ħ 2
𝐵= 2πε0 𝑟2
− 2𝑚𝑈2
∇2 𝑈2

A electron:
2 2
𝑒 1 ħ 2
𝐴= 2πε0 𝑟1
− 2𝑚𝑈1
∇1 𝑈1
2 2
𝑒 1 ħ 2
⇒ 𝑈1𝐴 = 2πε0 𝑟1
𝑈1 − 2𝑚
∇1 𝑈1
[This is the same hydrogenic equation we have solved earlier]
 25

100 1 𝑍 3 −𝑝1
𝑈1 (𝑟1) = π
(𝑎 ) 𝑒
0

B electron:
2 2
𝑒 1 ħ 2
𝐵= 2πε0 𝑟2
− 2𝑚𝑈2
∇2 𝑈2
2 2
𝑒 1 ħ 2
𝑈2𝐵 = 2πε0 𝑟2
𝑈2 − 2𝑚
∇2 𝑈2

[This is the same hydrogenic equation we have solved earlier]

100 1 𝑍 3 −𝑝2
𝑈2 (𝑟2) = π
(𝑎 ) 𝑒
0

100 100
Ѱ =𝑈 1
(𝑟1)𝑈 2
(𝑟2)

1 𝑍 3 −𝑝1 1 𝑍 3 −𝑝2
⇒Ѱ = π
(𝑎 ) 𝑒 π
(𝑎 ) 𝑒
0 0

1 𝑍 3 −(𝑝1+𝑝2)
⇒Ѱ = π
(𝑎 ) 𝑒
0
𝑍
− 𝑎 (𝑟1+𝑟2)
1 𝑍 3
⇒Ѱ = π
( 𝑎0
) 𝑒 0

𝑍
[𝑝 = 𝑎0
𝑟]

From this stage forth, we can get several types of methods to get an approximate value of
the energy of the atom.

Variational Method

Summary
This method is used to determine the energy of the system. In order to accomplish this, we
need to at first ignore the electron-electron repulsion terms. Then we will compute the
ground state of the wave function. Then the PDE can be made separable into two
hydrogenic equations. Then, the wave function of the equation would just be a sum of two
hydrogenic wave functions including the electron-electron repulsion force. Then we calculate
the expectation value of our original Helium schrodinger’s equation.

2 2 2
𝑒 1 1 ħ 2 2 𝑒
𝐸Ѱ = 2πε0
(𝑟 + 𝑟2
)Ѱ − 2𝑚
(∇1 + ∇2 )Ѱ − 4πε0𝑟12
1
2 2 2
𝑒 1 1 ħ 2 2 𝑒
⇒ < 𝐸Ѱ >=< 2πε0
(𝑟 + 𝑟2
)Ѱ >+<− 2𝑚
(∇1 + ∇2 )Ѱ >+<− 4πε0𝑟12
>
1

[In expectation form]

*
< 𝑥 >= ∫ Ψ (𝑥)Ψ𝑑𝑉
 26
A cheat way around this hardcore computation is that we can remember the fact that our
Schrodinger equation for helium has twice the hydrogenic part and a repulsion part. So, the
expectation energy equation can be transformed into this much nicer and simpler form:

2
𝑒
⇒ < 𝐸Ѱ >= 2 < 𝐻 >+<− 4πε0𝑟12
>

From previously, we deduced the equation for Hydrogen’s electron energy:

2 2
𝑍𝑒
𝐸𝑛 =− 2
8πε0𝑎0𝑛
2
𝑍
⇒ 𝐸𝑛 = − 13. 6 𝑒𝑉 ( 2 )
𝑛

As we are calculating for ground state and it’s an helium atom, thus: 𝑛 = 1, 𝑍 = 2

< 𝐻 >=− 4(13. 6𝑒𝑉)

2
𝑒
< 𝐸Ѱ >=− 108. 8𝑒𝑉 +<− 4πε0𝑟12
>

So, the only computation required is to solve for the electron electron repulsion term.

[Also, the 𝑟1, 𝑟2 are radius vectors.]

 27

Proposition
µ = 𝑐𝑜𝑠θ

Thus, the ground state energy for Helium atom is:

 28

This result is very close to the experimental value.

Perturbation Theory:
This method works by breaking our Hamiltonian into two parts.

Proposition:
𝐻 = 𝐻0 + 𝐻1
2 2 2 2
𝑒 1 ħ 2 𝑒 1 ħ 2
𝐻0 = 2πε0 𝑟1
− 2𝑚𝑈1
∇1 𝑈1 + 2πε0 𝑟2
− 2𝑚𝑈2
∇2 𝑈2
2
𝑒
𝐻1 =− 4πε0𝑟12

From the Variation method, we come to know that: 𝐻0 = − 8𝐸0

In other words, the Hamiltonian of the unperturbed part has the energy of eight hydrogens at
their ground state. So, we are left to compute the other part of the hamiltonian.

*
𝐸1 = ∫ Ψ 𝐻1Ψ𝑑𝑉

2
𝑒 2
⇒ 𝐸1 = ∫− 4πε0𝑟12
|Ψ| 𝑑𝑉
2
𝑒
2
1 | 1 𝑍 3 − 𝑎𝑍 (𝑟1+𝑟2)|
⇒ 𝐸1 = − ∫ | ( )𝑒 0 | 𝑑τ
4πε0 𝑟12 | π 𝑎0 |
| |
2
2 | 1 𝑍 3 − 𝑎𝑍 (𝑟1+𝑟2)|
⇒ 𝐸1 = ∫−
𝑒 | ( )𝑒 0 | (𝑟 2𝑑𝑟 𝑠𝑖𝑛θ 𝑑θ 𝑑ϕ 𝑟 2𝑑𝑟 𝑠𝑖𝑛θ 𝑑θ 𝑑ϕ )
4πε0𝑟12 | π 𝑎0 | 1 1 1 1 1 2 2 2 2 2
| |
3 3
[𝑑τ = 𝑑 𝑉1𝑑 𝑉2]
2 2
[𝑑τ = 𝑟1 𝑑𝑟1𝑠𝑖𝑛θ1𝑑θ1𝑑ϕ1𝑟2 𝑑𝑟2𝑠𝑖𝑛θ2𝑑θ2𝑑ϕ2]
5
⇒ 𝐸1 = − 2
𝐸0

𝐻 = 𝐻0 + 𝐻1
5
⇒ 𝐻 = 8𝐸0 − 2
𝐸0
11
⇒𝐻 = 2
𝐸0
⇒ 𝐻 =− 74. 8𝑒𝑉

Verdict:
From experiment, we get the experimental value of Helium’s ground state energy is:
− 79. 005151042(40) 𝑒𝑉. The approximations made by both methods lead to the result
of − 74. 8𝑒𝑉. They are at 6.335221155% range accuracy with the experimental readings.
 29
More better accuracy can be obtained if we choose/select a better trial function in both of
these cases.

Multi-Electron system wave functions:

First, we need to clear some definitions. Orbital means a region of space.
From Pauli’s exclusion principle, we came to know that an orbital can accommodate a
maximum of two electrons. Whereas the orbitals can be thought of as the magnetic
component of our wave function. So, instead of a pure analytical solution for the atomic
system, we will instead add wave functions as the probability of our electron’s existence.
Also it is to be noted that the actual analytical solution for our wave function is also not
feasible by any means, the reasons were described previously in the (Explanation of
unsolvability) section.

Slater determinant:

The above matrix determinant is used to determine the Quantum mechanical wave function
for a multi-electron system which constitutes ‘n’ electrons. Thus, all the possibilities of the
electron being in up or down spin are made to be in product, then on the left, we have the
normalization constant which keeps this wave function in the accurate scale of probability.

Here, the ‘χ’ wave function component for the respective electron. It’s variable ‘𝑥’ is the
position space of the orbital.

Intuition and derivation:

From Helium atom, we can see that we had to break our wave functions into two
components:

Now by rule wave-function, a particle may show antisymmetry. As electrons are

indistinguishable, identification or tracking of one electron’s wave is not possible. So, the
electrons may swap their orbitals. So the probability of finding one electron is equal to the
other. Thus, mathematically it follows the following identity:
∞ ∞
2

−∞
| | −∞
|
⇒ ∫ Ψ(𝑥1, 𝑥2) 𝑑∆𝑥 = ∫ Ψ(𝑥2, 𝑥1) 𝑑∆𝑥 |2
|
⇒ Ψ(𝑥1, 𝑥2) |2 = |Ψ(𝑥2, 𝑥1)|2
 30
[differentiate both sides]
⇒ Ψ(𝑥1, 𝑥2) =± Ψ(𝑥2, 𝑥1)

So, this shows that the wave function can be either symmetric or antisymmetric. But
electrons can actually show antisymmetric properties. Thus
If we break the other side, we will obtain the following equation:
− Ψ(𝑥2, 𝑥1) =− 𝑋1(𝑥2)𝑋2(𝑥1)
Thus, our general solution for our wavefunction for our Helium atom becomes:
Ψ(𝑥1, 𝑥2) = 𝑁[𝑋1(𝑥1)𝑋2(𝑥2) − 𝑋1(𝑥2)𝑋2(𝑥2)]
Here, there would yield a total of two terms. So, the normalization constant would become:
1
𝑁=
2!

From this Helium case, if we generalize this view to any system with ‘n’ electrons, then we
would conclude with the formula we found in the above section.

Significance:
First, we have discussed the derivation of Hydrogen atom’s wave function. The most
fundamental atomic system out there. It was relatively effortless because it was separable
and solvable. After a coordinate transformation and some differential equation tricks, it can
be solved relatively easily.

Now, when the discussion is on the Helium atom, which has a 3 body system, by three body
rule, it becomes analytically insolvable. So we need to choose some approximation methods
to find the ground energy of Helium. The determination of energy of the system at its
different states is very crucial for understanding and measuring thermodynamics. How atoms
behave with increment of temperatures. We need to know which reaction with which atom
would cause the increment of temperature by the exact quantity. So, we must find the energy
of the atom in its different states. All the approximate methods are a deviation of the word
“pseudo-eigenfunction” which means to choose a function which should be closest to the
experimental data. The method which can do this with the least amount of computation in
the most feasible time and with the most accuracy is chosen to be the best here. In our case,
the variational method was the best. Although in the modern world, various new techniques
have emerged to compute for better approximate energy values by the combination of one
or two methods.

Lastly, we need to discuss the wave function of the atom itself. As it is not possible to
separate the Helium’s schrodinger’s equation, we solve this by considering a Linear
combination of the atomic wave function and orbital space. Though they do not give us the
full wavefunction, they at least give us the result for the state required. This is extremely
important to get an idea of the physical property of the Helium atom. So, we can compute its
behavior while being in a molecule.
 31
Lastly, at the extreme we can scale these methods to any atoms of the periodic table and
thus we can discuss their thermal and physical properties. That’s all we need for explaining
chemical reactions.