Analytical solution for hydrogen atom by Schrödinger equation

Applied Mathematics Department

University of Science and Technology - Zewail City
INTRODUCTION TO ORDINARY DIFFERENTIAL EQUATIONS
MATH - 202

Supervisor:
Prof: Ahmed Abdelsamea
Prof: Waleed Abdelmeguid
Prepared by:
Mahmoud Ebaid, 201700442
Ahmed Elsehmawy, 202001919
Yossef Adel, 202001273

© Copyright 2022, Zewail City

Analytical solution for hydrogen atom by Schrödinger equation 1

Table of contents

Contents
Abstract........................................................................................................................................................ 3
Introduction ................................................................................................................................................. 3
Problem definition ...................................................................................................................................... 4
Methodology ................................................................................................................................................ 4
Results ........................................................................................................... Error! Bookmark not defined.
References .................................................................................................................................................... 6

Analytical solution for hydrogen atom by Schrödinger equation 2

Abstract

All earlier atomic models were built based on premises and assumptions of experimental results
besides imaginations of those scientists to find a suitable model that can manage their experimental
results within it. This was the dominant idea until Schrödinger was capable to derive his core
equation of quantum theory a wavefunction for a particle in addition to other quantum postulates
and theories, he had the ability to find hydrogen atom structure through rigorous mathematical
steps, in this paper we are going to investigate this analytical solution introducing it in details
giving the results there corresponding physical meaning.

Introduction
Atoms are the building blocks of all martials surrounding us, it has been addressed through human
history beginning from B.C. with Democritus at 450 B.C. he assumed that all matters around us
are made of tiny particles called “Atomos” meaning indivisibility of those particles [1]. 1083,
Dalton put his premises about atomic theory that all elements are made of atoms which are identical
for same material but not for different ones in addition to conservation of atoms or matter
conservation [2]. Michael Faraday also defined a statement that atoms have relation to electricity.
J.J Thomson conducted an experiment which led to discovery of particles which is then called
electrons are negatively charged. That discovery made Thomson to imagine atomic model like
plum pudding in which all electrons are distributed equally in a symmetrical positive charge [3].
Afterwards Malakian had the ability to estimate the mass and the charge of those electrons. At
1909, Rutherford’s experiment proved that JJ Thomson premises about atomic structure are invalid
otherwise the positive part is concentrated dense particle in the middle of atom structure supported
called nucleus by his experiment of gold foil [4]. Between 1887 and 1915, Henry Moseley
discovered that each nucleus has its own number of protons. Bohr Model which is similar to solar
system in which an electron orbit around the nucleus beside the quantization of its energy [5]. The
modern model is called quantum model of an atom in which electrons are probability of positions
forming orbital around nucleus beside that electrons can act as a wave or as particle by Schrödinger
around 1924 [6].

Figure 1: Timeline of atomic model.

Analytical solution for hydrogen atom by Schrödinger equation 3

Hydrogen atom has large significance through history besides other good reasons why to address
it. Hydrogen atom spectra is considered to be an innovative tool in technology and science in
addition to be a motivation for quantum theory. For example, electron transition in hydrogen atom
is used to examine the constant of fine structure’s stability over the time scale of cosmology.
Hydrogen atom or hydrogen like atoms has one electron orbiting around nucleus which could be
single proton in case of hydrogen or multiple protons in case of other atoms. This is similar to
particle [electron] in a box but with spherical potential and coordinates and soft walls. Hydrogen
atom or hydrogen like atoms is the corner stone for quantum theory since it is the only atom can
be solved analytically by Schrödinger equation for wave functions otherwise all atoms are solved
asymptotically [7].

Problem definition
Using Schrödinger equation of wave function to solve hydrogen atom analytically to find the exact
real structure of atoms through organized defined mathematical steps.

Methodology
The hydrogen atom:
It is the only atom that can be solved exactly. The results become the basis for understanding all
other atoms and molecules.
Classically we have the following picture,
𝑷e𝟐 𝑷p 𝟐 𝒆𝟐
𝑬 = 𝟐𝒎 + − |𝒓⃗⃗⃗ −𝒓⃗⃗⃗ |
e 𝟐𝒎p e p

(Total energy = K.E of electron + K.E of proton + potential energy

of proton and electron due to then mutual coulomb attraction)
Thus, we can write the following Hamiltonian for the hydrogen
atom: (equation 1)
ℏ𝟐 ℏ𝟐 𝒆𝟐
𝑯= 𝛁 e𝟐 + 𝛁p𝟐 −
𝟐𝒎e 𝟐𝒎p |𝒓 𝒓p|
⃗⃗⃗e − ⃗⃗⃗
𝛁e𝟐 Operates only on the electron coordinates.
𝛁p𝟐 Operates only on the proton coordinates.
This Hamiltonian describes not only the behavior of the electron and proton due to coulomb
interaction but also any motion the atom makes. To distinguish between these two harts of the
motion we use a Centre-of-mass coordinate system.
Therefor we obtain two equations of motions, one describing the motion of the Centre-of-mass in
laboratory coordinate system, the other the motion of the parts of the system relative to their
Centre-of-mass.

Analytical solution for hydrogen atom by Schrödinger equation 4

The coordinates for the Centre-of-mass are:
𝒎e𝒙e+𝒎p𝒙p 𝒎e𝒚e+𝒎p𝒙p 𝒎e𝒛e+𝒎p𝒛p
𝑿= ,𝒀 = ,𝒁 =
𝒎e+𝒎p 𝒎e+𝒎p 𝒎e+𝒎p

On the vector:
𝒙
𝒚 ⃗ e + 𝒎p𝒓
𝒎e𝒓 ⃗p
⃗⃗ = ( ) =
𝑹
𝒛 𝒎 e + 𝒎p

The coulomb force between the proton and the electron depends only on their distance from each
other, so we introduce the vector
𝒙
⃗ = (𝒚) = 𝒓
𝒓 ⃗e−𝒓
⃗p
𝒛

To carry out transformation of equation (1) to the Centre-of-mass coordinates, we form

𝝏𝑿 𝒎e 𝝏𝑿
= 𝒎 +𝒎 , 𝝏𝒙 = 𝟏
𝝏𝒙e e p e

𝝏⍦(𝑿, 𝒙) 𝝏⍦ 𝝏𝑿 𝝏⍦ 𝝏𝒙 𝒎e 𝝏⍦ 𝝏⍦
= + = +
𝝏𝒙e 𝝏𝑿 𝝏𝒙e 𝝏𝒙 𝝏𝒙e 𝒎e + 𝒎p 𝝏𝑿 𝝏𝒙
𝝏⍦ 𝒎p 𝝏⍦ 𝝏⍦
= −
𝝏𝒙p 𝒎e + 𝒎p 𝝏𝑿 𝝏𝒙

Analogous expressions are obtained for:

𝝏⍦ 𝝏⍦ 𝝏⍦ 𝝏⍦
, , , 𝒂𝒏𝒅
𝝏𝒚e 𝝏𝒛e 𝝏𝒚p 𝝏𝒛p
Define the reduced mass:
𝒎e𝒎 p
µ=
𝒎e + 𝒎p
We get:
µ µ
𝛁e = 𝛁R + 𝛁, 𝛁p = 𝛁R − 𝛁
𝒎p 𝒎p
Where ( 𝛁R) operates only on coordinates of the Centre-of-mass and ( 𝛁 ) works only on the
coordinates x, y, z.

Analytical solution for hydrogen atom by Schrödinger equation 5

The Hamiltonian H becomes: (equation 2)
−ℏ𝟐 µ 𝟐 ℏ𝟐 µ 𝟐 𝒆𝟐
𝑯= ( ⃗⃗ R + 𝛁
𝛁 ⃗⃗ ) − ( ⃗ R−𝛁
𝛁 ⃗) −
𝟐𝒎e 𝒎p 𝟐𝒎p 𝒎e r
−ℏ𝟐 µ𝟐 µ ℏ𝟐 µ𝟐 µ 𝒆𝟐
𝑯= [ 𝛁 R
𝟐
+ ⃗⃗⃗⃗
(𝛁 R ⃗𝛁 + 𝛁
⃗𝛁⃗ R) + 𝛁 𝟐 ] − [ 𝛁 R
𝟐
− ⃗⃗⃗⃗
(𝛁 R ⃗𝛁 + 𝛁
⃗𝛁⃗ R) + 𝛁 𝟐 ] −
𝟐𝒎e (𝒎p)𝟐 𝒎p 𝟐𝒎p (𝒎e)𝟐 𝒎e r

−ℏ𝟐 ℏ𝟐 𝒆𝟐
𝑯= 𝛁R𝟐 − 𝛁−
𝟐(𝒎e + 𝒎p) 𝟐µ r

References
[1] “Atomic Theory - an overview | ScienceDirect Topics.”
[Link]
(accessed May 16, 2022).
[2] “Dalton’s atomic theory (article) | Khan Academy.”
[Link]
atomic-structure/a/daltons-atomic-theory-version-2 (accessed May 16, 2022).
[3] “Discovery of the electron and nucleus (article) | Khan Academy.”
[Link]
atomic-structure/a/discovery-of-the-electron-and-nucleus (accessed May 16, 2022).
[4] “Gold Foil Experiment | CK-12 Foundation.” [Link]
chemistry-flexbook-2.0/section/4.14/primary/lesson/rutherfords-atomic-model-chem/
(accessed May 16, 2022).
[5] “5.6: Bohr’s Atomic Model - Chemistry LibreTexts.”
[Link]
(CK-12)/05%3A_Electrons_in_Atoms/5.06%3A_Bohr’s_Atomic_Model (accessed May
16, 2022).
[6] “The quantum mechanical model of the atom (article) | Khan Academy.”
[Link]
orbitals/a/the-quantum-mechanical-model-of-the-atom (accessed May 16, 2022).
[7] “QUANTUM MECHANICS: A TEXTBOOK FOR UNDERGRADUATE - MAHESH C.
JAIN - ‫ كتب‬Google.”
[Link]
&q&f=false (accessed May 16, 2022).

Analytical solution for hydrogen atom by Schrödinger equation 6