Chapter 6

The hydrogenic atom

A one-electron atom or ion that has only one

electron and a nucleus of charge Ze.
• Hydrogen atom is a nucleus of mass
mn and charge +e (a single proton) and
an electron of mass me and charge -e
“in orbit” about the nucleus.

• The description of the hydrogen atom

is the same as for the 3-D rigid rotor
except now r can vary from 0 to ∞.
• The potential energy V is not zero
• V is an interaction between the
electron and the nucleus for this system
 • The Coulomb potential energy (Z = 1):
���
• � =− V depends only on the distance r not the angles � or �
���� �

• e = 1.6×10-19 C, �0 = 8.85419×10-12 C2/J.m or C2 /N. m2 ,

• r is the distance between the electron and the proton.

• As with the 3-D rotational motion, The acceptable wavefunctions �(�, �, �)

are separable into three functions that depend only on r, on �, and on �:
•
• �(�, �, �) = �(�)�(�)�(�)
• Since the mass of the electron is so much less than that of the proton, so � = me.
• The Hamiltonian operator is:
ℏ� �
� � � � � � � ��
• � =− � � + ��� � + +
��� � �� �� �� ��� � �� �� �� ���� � ���
�(�)
The Schrödinger equation becomes
ℏ2 1 2 �� 1 � � 1 �2
− 2 � + ��� � + +
2�� � �� �� �2 ��� � �� �� �2 ���2 � ��2
�(�) �(�, �, �) = ��(�, �, �)

We will use the separation technique to simplify and solve this

equation
 • Multiply through by 2�� �2 to obtain:
2 � 2 � � � � �
•−ℏ � �(�, �, �) − ℏ ��� � +
�� �� ��� � �� ��
� ��
�(�, �, �) + 2�� �2 [�(�) − �]�(�, �, �) = 0
���� � ���
• The first and third terms depend only on r variable .
• The second part depend upon only � and � .

• Therefor the last eqn. can be rearranged as:

2 � 2 � � � �
• −ℏ � �(�) + 2�� �2 [�(�) − �]�(�) = ℏ� ��� � +
�� � �� ��� � �� ��
� �
�(�, �)
���� � ���
• This is valid only if both sides equal a constant

• The wavefunction �(�, �) is the spherical harmonics, discussed in the

3-D rotation. These solutions impose two quantum numbers, l and m,
where, � = 0, 1, 2, … and � = 0, ± 1, ± 2, … ± �.

• The spherical harmonics (�(�, �)) are eigenfunctions of �2

� � � � � ��
•ℏ ��� � + �(�, �) =
��� � �� �� ���� � ���
2 �(�+�)ℏ�
• � �(�, �) = (��� ��������)
��� ��
The Radial Equation and Radial wavefunction R(r)
� � � � � �(�+�)ℏ�
• Therefore − ℏ � �(�) + ��� � [�(�) − �]�(�) =
�� �� ��� ��
• This equation is used to calculate and interpret the total energy E (the
sum of a radial KE, an angular KE, and PE).
• The above equation contains the quantum number l is present.
• This suggests its solution depends on the quantum number l.

• The normalized radial wavefunctions are given by:

•
� � �
(�−�−�)! � �+ −
� � ��+� ��
• ��� (�) =− �
� � ���
��+�
��[(�+�)!]� ��� ���
• where � ≥ � + 1, so, � = 1, 2, 3, …, and � = 0, 1, 2, …, � − 1
 3
− ��� (�) depend on two quantum � 2
• �01 (�) =2 �−�
numbers n and l �0

- The �2�+1 •
�+1 are polynomials called 3
�
associated Laguerre polynomials • �02 (�) =
2
(2 − �)�−�/2
2�0
- � = Zr /a0 •
���� ℏ� 3
- a0 = �� ��
is the Bohr radius
• �12 (�) =
1 � 2
��−�
3 2�0
The complete wavefunctions are

���� (�, �, �)
1
= ��� (�) ��
� (�) ����
2�
• The first few normalized wavefunctions of the hydrogenic atom are:
3
1 � 2
• �100 (�, �, �) = �−�
� �0
•
3
1 � 2
• �200 (�, �, �) = (2 − �)�−�/2
4 2� �0
•
3
�
1 � 2 −
• �210 (�, �, �) = �� ��� �
2
4 2� �0
•
3
�
1 � 2 −
• �21±1 (�, �, �) =± �� ��� ��±��
2
4 2� �0
 The allowed energies are:
�� �� ��
• �� =− = − , � = �, �, �, … ,a0 = 0.529Å
���� �� �� ���� �� ��
•
• For any hydrogenic atom, the energy is:
�� �� �� �� ��
• �� =− = − , � = �, �, �, …
���� �� �� ���� �� ��
•
• The negative energy is due to the interaction of oppositely charged particles
contributes to a decrease in energy.
• The total energy is quantized and depends only on n but does not depend on
m or l.
• The degeneracy of energy level with quantum number n is n2-fold degenerate.
• Because the permissible values of l are l = 0, 1, . . ., n-1, and for each value of l
there are values 2l+1 of m “m = 0, ± 1, ±2, ... ±l”
 • The difference in energy between two energy levels n1 and n2 is:
•
�� �� � �
• ∆� = �� − �� = −
���� �� ��� ���
• In terms of wavenumber �, the above equation becomes:
�� �� � � � �
• �= − = �� −
���� ��� ��� ��� ��� ���

• �� ���� (�, �, �) = �(� + �)ℏ� ���� (�, �, �)

•
• �� ���� (�, �, �) = �ℏ���� (�, �, �)
•
Calculate the energy values for the first three shells of H atom.
�
�.�× ��−�� �� �.�× ��−�� �
• �� =− � �
=− �. ��� × ��−�� �
� �
� �.�����× ��−�� �.���× ��−�� �.� (�)�
�.�
•
•
�
�.�× ��−�� �� �.�× ��−�� �
• �� =− � �
=− �. ��� × ��−�� �
� �
� �.�����× ��−�� �.���× ��−�� �.� (�)�
�.�
•
•
�
�.�× ��−�� �� �.�× ��−�� �
• �� =− � =− �. ��� × ��−�� �
−�� �� �
� �.�����× �� �.���× ��−�� �.� (�)�
�.�
The three quantum numbers : Shells and subshells
 n ( principal quantum number ) 1, 2, 3....
 indicates the energy of the electron and the average distance of an
����
electron from the nucleus �� = −
���� �� ��
 Each group of wavefunctions having the same value of n defines a shell.
Shells with n = 1, 2, 3 . . . are commonly referred to as K, L, M, . . . shells.

• As n increases, the average distance of an electron from the nucleus

increases.

• Determine the No. of subshells in each principal shell

• Each principal shell has n subshells
• An electron that is closer to the nucleus is attracted more
strongly than an electron that is farther out in space.

• The electrons with higher values of n are easier to remove from

an atom (low Ionization Potential IP).

• All wave functions of the same n are said to constitute a

principal shell. Those electrons have similar average distances
from the nucleus.

• The principal quantum number n corresponds to the n used by

Bohr to describe electron orbits.
 The Azimuthal Quantum Number (l)

It describes the shape of the region of space occupied by electron.

All wave functions have the same n and l values form a subshell.

The regions of space occupied by electrons in the same subshell

usually have the same shape, but they are oriented differently in
space.
These subshells are generally referred to by lower-case letters. l= 0 being
denoted by s , l = 1 by p, l = 2 by d, l = 3 by f

The allowed values of l (No. of subshells) depend on the value of

n and can range from 0 to n − 1: l=0,1,.,2,3,..(n−1)
[n subshells]
It is used to calculate the total angular momentum of
electron in subshell
� = �(� + �)ℏ
It is also used to calculate an angular KE, and PE of subshell
�(�+�)ℏ�
El =
��� ��
It is also used to determine the No. of orbitals (possible,
directions , orientations) in each subshell
2l + 1

How many subshells and orbitals are contained within the

principal shell with n = 4?
 The Magnetic Quantum Number (m)

It describes the orientation of the region of space occupied by

an electron with respect to an applied magnetic field.

The value of m describes the orientation of the region in space

occupied by an electron.

The allowed values of m depend on the value of l:

m can range from −l to l in integral steps (2l + 1 value):
m=−l,−l+1,...0,...l−1,l

For example, if l=0, m =0; if l = 1, m can be −1, 0, or +1;

and if l = 2, m can be −2, −1, 0, +1, or +2.
 It is used to calculate the total angular momentum of
electron in certain the orientation

 The z component of the angular momentum is determined

completely by m through:
• �� = �ℏ

It is also used to calculate an angular KE in certain direction

��ℏ�
Em =
��� ��
Each wave function with an allowed combination of n, l,
and m values describes an atomic orbital

A wave function with an allowed combination of n, l and m

quantum numbers determine a particular spatial distribution
for an electron.

For a given set of quantum numbers, each principal shell has a

fixed number of subshells, and each subshell has a fixed number
of orbitals

The number of orbitals in a shell of n is n2, so in a hydrogenic

atom each energy level is n2-fold degenerate
In the absence of a magnetic field,
each energy level has a
degeneracy of 2l + 1 for a given n
and l.

In the presence of a magnetic

field, these levels split, and the
energy depends upon the particular
value of m.

This splitting is called the Zeeman

effect.

In this case, E is a function of both

the quantum numbers n and m.
Allowed values of n, l, and m through n = 4
n l Subshell Designation m Number of Number of
Orbitals in Orbitals in
Subshell Shell
1 0 1s 0 1 1
2 0 2s 0 1 4
1 2p −1, 0, 1 3
3 0 3s 0 1 9
1 3p −1, 0, 1 3
2 3d −2, −1, 0, 1, 2 5
4 0 4s 0 1 16
1 4p −1, 0, 1 3
2 3d −2, −1, 0, 1, 2 5
3 4f −3, −2, −1, 0, 1, 2, 3 7
• Orbitals are designated by pairing
the value of n and the letter
representing the value of l:
• 1s, 2s, 2p, 3s, 3p, 3d, and so forth.

• A wavefunction with n = 1 and l = 0

is called a ls wavefunction (��� );
one with n = 2 and l = 0 is called a
2s wavefunction (��� ), and so on.

• A numerical subscript can be used to

label the m values of the individual
orbitals: 2p-1, 2p0, 2p+1, and so on.
 Hydrogen-like atomic wavefunctions for n values 1,2,3: Z is the atomic number of the
nucleus, and ρ=Zra0, where a0 is the Bohr radius and r is the radial variable

n ℓ m Radial Component

n=1 ℓ=0
m=0 ψ100=1/√π (Z/a0)3/2e−ρ
n=2 ℓ=0 m=0 ψ200=1/√32π (Z/a0)3/2e−ρ/2 (2−ρ)
ℓ=1 m=0 ψ210=1/√32π (Z/a0)3/2e−ρ/2 ρ cos(θ)
ℓ=1 m= ±1 ψ21±1=1/√64π (Z/a0)3/2e−ρ/2 ρ sin(θ) e± iϕ
n =3 ℓ=0 m=0 Ψ300=1/(81√3π) (Z/a0)3/2e−ρ/3 (27−18+2ρ2)
ℓ=1 m=0 Ψ310=(1/81)(√2/π) (Z/a0)3/2e− ρ/3 (6r-ρ2) cos(θ)
ℓ=1 m= ±1 Ψ31±1=1/81√π (Z/a0)3/2e−r/3 (6ρ--ρ2)sin(θ) e± iϕ
ℓ=0 m=0 Ψ320=1/81√6π (Z/a0)3/2e− ρ/3 (ρ2)(3cos(θ)2-1)
ℓ=2 m=± 1 Ψ32±1=1/81√π (Z/a0)3/2e− ρ/3 ρ2cos(θ) sin(θ) e± iϕ
ℓ=2 m= ±2 Ψ32±1=1/162√π (Z/a0)3/2e− ρ/3 ρ2 sin2(θ) e± iϕ
 The hydrogen atom wavefunctions
Different types of probabilities

• Graphs of the radial wavefunctions of the first few states of the hydrogen
atom
• The radial wavefunctions is zero at r = 0, except for s states
• The number of nodes in the radial wavefunction is equal to n-l-1.
• The ns states are spherically symmetric because there is no angular
dependence.
• The probability density for the electron in a volume element
�� (�� = � 2 sin� d� d� d�) at a point (r, θ, and ϕ ) is ( � � )
• The probability density �1� 2 depends only on r i.e. it is spherically
symmetric.
• Plot of ��� � of the electron versus the radial distance r shows that
its maximum value at the nucleus, r = 0, ( ��� � = 1/πa3),
• The probability density decreases exponentially with r.
• The chance that the electron lies in a small volume element very near
the nucleus is larger than that it lies in the same size at a greater
distance from the nucleus.
 At what distance from the nucleus is the electron
most likely to be found?
• consider the probability of finding the
electron anywhere between the two
walls of a thin spherical shell of
thickness dr at a radius r, regardless of
the values of � and � “i.e. between r
and r + dr” is given by

�� �
• [��� (�)]2 � 2 d� � �
(��� (�, �) � ���� �� ��

• The radial distribution function

• A thin spherical shell of inner and
outer radii r and r + dr
• = [��� (�)]� ��
A plot of the radial distribution function �2 [��� (�)]2 versus
distance from the nucleus for the hydrogen atom
The radial p��������� ����� [��� (�)]� for the hydrogen atom
• There is a distance at which the electron is most likely to be found
where the radial distribution function passes through a maximum .

• For ls state the probability starts at zero, increases to a maximum,

then decreases toward zero as the radius gets larger and approaches
infinity

• Both of 2s and 3s orbits have noticeable probability density at regions

nearer the nucleus than p or d orbits
• For the 2s orbital in hydrogen atom, the most probable radius is
(3+ 5)a0/Z. This larger value reflects the expansion of the atom as its
energy increases.
•.
• The existence of Nodes in orbitals due to the wave nature
• In the Bohr model, the electron is incorrectly restricted to lie in
fixed, well-defined orbits. The difference between the two models is
attributable to the wavelike behavior of the electron and the
Heisenberg uncertainty principle.

• Quantum mechanics shows that an electron doesn’t have a specific

distance from the nucleus. Instead, it can have a range of distances
having differing probabilities. It does have a most probable distance
Show that the most probable value of r of the electron in a 1s
orbital of a hydrogen atom is a0.
• Dfferentiate the radial distribution function with respect to r and set
the result equal to 0,
2�
�
([��� (�)]2 �2 ) =
� 4 2 −�0
• � � =0
�� �� �30
2� 2�
4 − 2 2 4 −
• = (2�)( � �0 ) + (� )(− )( � �0 )
�30 �0 �30
2� 2�
4 − 2 4 −
• (2�) 3�
�0 = (�2 )( )( � �0 )
�0 �0 �30
•
• ��� = �0
• Calculate the probability that an electron in a hydrogen atomic l s
within one Bohr radius of the nucleus.
•
• Answer:
2�
�0 �( ) 2 2 �0 4 −
• Prob (0 ≤ � ≤ �0 ) = �0 �2 ��
0
[� � � ] � �� = 0 �30
�
•
4
2�
− �2 �0 2��0 2 2�0 3 �0
•= � �0 − − −
�30 2 4 8 0
•
−2 5 1
•=4 � − − − = 0.323
4 4
 Total probability in three-dimension
• (���� (�, �, �) � �� = [��� (�)]� (��� (�, �) � � � ���� �� �� ��
• A common way to present the angular functions is as three-
dimensional figures.
The complete ns wavefunctions are spherically
symmetric because there is no angular
dependence in the wavefunction, that
wavefunction has the same value for
every choice of (�, �),
Three-dimensional polar plots of the angular part of the real
representation of p and d orbitals
• Individual p, d, … subshells are not spherical and do have angular
dependence.
• The three-dimensional plots show that The angular distributions of the
p and d subshells lend the “dumbbell” and “rosette” descriptions to the
p and d orbitals, respectively
• For each p orbital, there is one plane where the electron probability is
zero, nodal planes or nodal surfaces
Nodal planes for p and d orbitals. Each p orbital has one nodal
plane. Each d orbital has two nodal planes. The dz2 orbital has
two nodal cones
 Electron cloud
• The quantity �∗ � �� is the probability
that the electron is located within the
volume element �� at a point (r, θ, and
ϕ ). the density of dots

• The area where the dots represent the

highest density represents the regions
where the electron is found most of the
time.
• If we picture the dots as representing
particles of a cloud “electron cloud”, we
say that the cloud has its highest density
where the dots are closest together.