The Hydrogen Atom

■ Atom is a 3D object, and the electron motion is

three-dimensional. We’ll start with the simplest
case - The hydrogen atom.
■ An electron and a proton (nucleus) are bound
by the central-symmetric Coulomb interaction.
■ Because mp>>me, we neglect the proton motion
■ Thus, we can treat this problem as the motion of
an electron in the 3D central-symmetric Coulomb
potential.
Three dimensions – we expect that the motion
will be characterized with three quantum U  U r   
e2
numbers. 4 0 r

The task: solve the time-independent Schrödinger

equation for E< 0 (bound state), find the energy
eigenvalues (the spectrum) and eigenfunctions
(stationary states).

Dr. Sabry El-Taher 1

The H-atom is the only atom that can be solved
exactly. The results become the basis for
understanding all other atoms and molecules.

For the hydrogen atom the Schrödinger equation:

K V   E
has a spherically symmetric potential energy:

1 e2
V  V (r )  
4 0 r - distance from r  x2  y2 z2
origin to point P z
For Hydrogen-like atoms (He+ or Li++),   cos1
replace e2 with Ze2. - Zenith (polar) angle r
The potential V(r) does not depend on either  1 y
  tan
or  hence, it is most convenient to work in - Azimuthal angle
x
spherical polar coordinates, this will allow us to separate variables.
In addition, the spherical geometry of the model suggests the use of a spherical
Polar coordinate system.
Dr. Sabry El-Taher 2
 Time-independent Schrödinger Equation
in Polar Coordinates:
In all cases, for better accuracy, replace m with me m p
the reduced mass, .

me  m p

 2  x , y ,z   2  x , y ,z   2  x , y ,z  
2
     V  x , y ,z   x , y ,z   E  x , y ,z 
2  x 2
y 2
z 2


 2  x , y , z   2  x , y , z   2  x , y ,z 
 
x 2
y 2
z 2

1   2   r , ,   1     r , ,   1  2  r , , 
 r   2 sin   2 2
r r  r  r sin      
2 2
  r sin
2
 2  E V  r , ,    r , ,   0
Dr. Sabry El-Taher 3
Separation of Variables
 The wave function  is a function of r, , . This is a potentially
complicated function.
 Assume instead that  is separable, that is, a product of three
functions, each of one variable only:

  r , ,   R  r  f   g  

This would make the solution of the Schrödinger equation for

H- atom much simpler.

Dr. Sabry El-Taher 4

Solution of the Schrödinger Equation
for Hydrogen Atom
Start with Schrodinger’s Equation:

Substitute:

Multiply both sides by r2 sin2 / R f g:

Dr. Sabry El-Taher 5

 r and  appear only on the left side and  appears only on the right
side.
 The left side of the equation cannot change as  changes.
 The right side cannot change with either r or .

 Each side needs to be equal to a constant for the equation to be

true.
 Set the constant to be -mℓ2

Azimuthal equation

Dr. Sabry El-Taher 6

 Now set the left side equal to -mℓ2:

-mℓ2

Rearrange it and divide by sin2():

Now, the left side depends only on r, and the right side
depends only on . We can use the same trick again!
Dr. Sabry El-Taher 7
 Set each side equal to the constant ℓ(ℓ + 1):

Radial equation

Angular equation

In addition to the azimuthal equation

d 2g
 m l g 0
2 Azimuthal equation
 2

We’ve separated the Schrödinger equation into three one-dimensional

second-order differential equations, each containing only one variable.

Dr. Sabry El-Taher 8

Solution of the Radial Equation

The radial equation is called the associated Laguerre equation and

the solutions R are called associated Laguerre functions. There are
infinitely many of them, for values of n = 1, 2, 3, …

Assume that the ground state has n = 1 and ℓ = 0. Let’s find this
solution. The radial equation becomes:

The derivative of yields two terms:

Dr. Sabry El-Taher 9

 Try a solution
A is a normalization constant.
a0 is a constant with the dimension of length.
Take derivatives of R and insert them into the radial equation.


 

To satisfy this equation for any r, both expressions in parentheses

must be zero.
Bohr radius
Set the second expression
equal to zero and solve for a0: 
Set the first expression equal
to zero and solve for E: 
Both are equal to the Bohr results!
Dr. Sabry El-Taher 10
 Principal
Quantum
Number n
There are many solutions to the radial wave equation, one for each
positive integer, n.
The radial quantum number n gives the quantized energy En:

n = 1, 2, 3, …

Lowest energy (ground state energy): E0 = -13.6 eV.

Energy levels of the  Z 2e 4 A negative energy means

En   2 2 2 that the electron and
hydrogen atom:
8 0 h n proton are bound
together.
In the course of solving the radial equation, n occurs naturally and must satisfy
The condition that n  l  1 which is usually written as:
Dr. Sabry El-Taher 0  l  n  1, n  1,2,3, 11
The solutions of the radial wave equation depend on two quantum
numbers n and l and are given by:

1/ 2

 (n  l  1)!    2 
l 3 / 2
 2r 
 r / na0 2 l 1
R nl (r )   3  
l
r e L n l  
 2n  n  l  ! 
   na0   na0 

Where the L n2ll 1 (2r / na0 ) are called associated Laguerre polynomials.

The first few solutions for the radial equation are given in Table 7.1
The functions given by the above equation are just a polynomial
multiplied by an exponential.

Dr. Sabry El-Taher 12

Hydrogen Atom Radial Wave Functions

Dr. Sabry El-Taher 13

Solution of the Angular and Azimuthal Equations

The solutions to the azimuthal equation are:

satisfies the azimuthal equation for any value of mℓ.

The solution must be single-valued to be a valid solution for any :

Specifically:
So:

mℓ must be an integer (positive or negative) for this to be true.

Dr. Sabry El-Taher 14
 1 im l 
g m l    e
2
Must be single-valued (Born conditions).

 = 0 and  = 2 are same point.

For arbitrary value of m:

e im l   1 for   2 but e im l   1 for   0

e i 2  cos 2  i sin 2  1
e i 2  1 if m is a positive or negative integer or 0
Therefore, e im l   1 if   0
e im l   1 if   2 Only if m l  0,  1,  2,  3
wavefunction is single-valued only if ml
is a positive or negative integer or 0.

Dr. Sabry El-Taher 15

 1 iml 
g ml    e where m l  0,  1,  2,  3
2
ml is called the magnetic (azimuthal) quantum number.

The functions having the same |m| can be added and subtracted to
obtain real functions.
1
 0    m0
2
1
 m    cos m 

m  1, 2, 3
1
 m    sin m 


The cos function is used for positive m’s and the sin function is
used for negative m’s.
Dr. Sabry El-Taher 16
Solution of the Angular and Azimuthal Equations
Solutions to the angular and azimuthal equations are linked
because both have mℓ.

Physicists usually group these solutions together into functions

called Spherical Harmonics:

The radial wave function R and the spherical harmonics Y determine

the probability density for the various quantum states. The total
wave function depends on n, ℓ, and mℓ.

The wave function becomes

Dr. Sabry El-Taher 17

The spherical harmonics
The spherical harmonics are solutions of the angular Hamiltonian.
The spherical harmonics are the product of the solutions to the
angular and azimuthal equations.

With normalization, these solutions are:

Y (,) = N P (cos )e im

l
m
lm l
|m|

The m quantum number corresponds to the z-component of

angular momentum l.
The normalization constant is:
1/2
2l + 1 (l – |m|)!
N lm =
2 (l + |m|)!
Dr. Sabry El-Taher 18
The form of the spherical harmonics
Including normalization, the spherical harmonics are:

Y00 = 1 These functions describe the

4 angular distribution of atomic
0 3 cos orbitals.
Y1 = 4
Y1±1 = 3 sine ±i
8 The degeneracy (number of
m values) of a given orbital
Y =0 5 3cos 2 – 1 is 2l+1 and the angular
2
16 momentum of the electron
Y =±1 15 sincose ±i is [l(l + 1)h]1/2.
2
8
Y22 = 15 sin 2e ±2i
32
Dr. Sabry El-Taher 19
Normalized
Spherical
Harmonics

Dr. Sabry El-Taher 20

Dr. Sabry El-Taher 21
Have solved three one-dimensional equations to get

Rn ( r )
f m ( )
g m ( )
The total wavefunction is:

nlm (r ,  , )  g m ( )f lm ( )R nl (r )
n  1, 2, 3
 n  1, n  2, 0
m  ,  1   

Dr. Sabry El-Taher 22

Hydrogen atom wavefunctions - orbitals
1
For n =1: 1s orbital  1s  Ae  r /a0
A
a 3
0
a0 = 0.529 Å the Bohr radius
The wavefunction is the probability amplitude. The probability is the absolute
valued squared of the wavefunction.

 1 s  A2e 2 r/a
2 0 This is the probability of finding the electron a distance
r from the nucleus on a line where the nucleus is at r = 0.
1.4 2

1.2
1.5

1
2
0.8 note scale difference
1
0.6

0.4 0.5
0.2

0.5 1 1.5 2 2.5 3 0.2 0.4 0.6 0.8 1 1.2 1.4

r (Å) r (Å)
Dr. Sabry El-Taher 23
Copyright – Michael D. Fayer, 2007
For n = 2:
1
 2 s  B(2  r/a0 )e  r/2 a0
B Probability
4 2 a03 amplitude

When r = 2a0, this term goes to zero. a0 = 0.529, the Bohr radius
There is a “node” in the wave function.
2
 2 s   B(2  r/a0 )e  r/2 a0

2 Absolute value of the wavefunction
squared – probability distribution.

0.25
0.5

0.2
0.4
2
 0.3 0.15

node 0.1
node
0.2

0.1 0.05

2 4 6 8 1 2 3 4

r (Å) r (Å)
Dr. Sabry El-Taher 24
Wavefunctions for Hydrogen-like Atoms

Dr. Sabry El-Taher 25

Wavefunctions for Hydrogen-like Atoms

Dr. Sabry El-Taher 26

 The Radial Distribution Function

0.15

R2p2 0.10

R3p2 0.05

R3d2
0.00

0 2 4 6 8 10
vals.1

r/ao
( r R2P2 R3P2 R3D2 )

Is the most probable value of r for an electron in a hydrogen

2p orbital the maximum in R2p2 ?
No!! Relative values of R2p2 represent the relative probability
of finding an electron at this value of r for a specific pair
of values of  and .
To obtain the relative probability of finding an electron at a given
value of r and any angle, one must integrate * over all values
of  and .
Chapter 6: Slide 27
 We’ll use RDF(r)  P(r)

0.3

RDF1s 0.2

RDF2s
RDF3s 0.1

0.0

0 2 4 6 8 10
vals.1

r/a0
( r RD1S2 RD2S2 RD3S2 )

This is because:
RDF1s has 1 maximum R1s has no nodes
RDF2s has 2 maxima R2s has 1 node
RDF3s has 3 maxima R3s has 2 nodes

Chapter 6: Slide 28
 We’ll use RDF(r)  P(r)

0.3

RDF1s 0.2

RDF2p
RDF3d
0.1

0.0

0 2 4 6 8 10
vals.1

r/a0
( r RD1S2 RD2P2 RD3D2 )

This is because:
RDF1s has 1 maximum R1s has no nodes
RDF2p has 1 maximum R2p has no nodes
RDF3d has 1 maximum R3d has no nodes

Chapter 6: Slide 29
 Most Probable Value of r

0.3

RDF1s 0.2

RDF2p
RDF3d
0.1

0.0

0 2 4 6 8 10
vals.1

r/a0
( r RD1S2 RD2P2 RD3D2 )

The most probable value of the distance from the nucleus, r, is

given by the maximum in the Radial Distribution Function, P(r)  RDF(r)

It can be computed easily by: 

2
dP(r ) d Br R(r ) 2
 0
dr dr

Chapter 6: Slide 30
The wavefunction for an electron in a 
Zr

2pz orbital of a hydrogenlike atom is:  2 p z  Are cos( )

2 a0

We will determine the most probable distance of the electron

from the nucleus, rmp.
2

2

Zr
 
Zr

P(r )  Br R  Br re
2 2 2 a0   Br 4e a0
 
 

d  4  a0 
Zr

Br e  0 when r  rmp

dr  


 d   Zr   Zr dr 4    
Zr Zr

  B r   e  e 4r 
Z  
0  B r 4 e   e
a 0 a 0 4 a 0 a 0 3

 dr  
 dr 
   a0  

Chapter 6: Slide 31
  4  Z   Zr Zr
   Zr
Zr

 

0  B r   e a0  e a0 4r 3   Br 3e a0   4
  a0    a0 

Zrmp
Therefore:  40
a0

4 a0
rmp 
Z

One gets the same result for any 2p orbital because the
Radial portion of the wavefunction does not depend on m.

Chapter 6: Slide 32
 0.3

RDF1s 0.2

RDF2p
RDF3d
0.1

0.0

0 2 4 6 8 10
vals.1

r/a0
( r RD1S2 RD2P2 RD3D2 )

By the same method, one may calculate rmp for 1s and 3d electrons:
a0
rmp (1s )  These most probable distances correspond to
Z predicted radii for the Bohr orbits:
4 a0
rmp ( 2 p )  a0
Z rn  n 2
Z
9 a0
rmp (3d ) 
Z

Chapter 6: Slide 33
 Atomic orbitals
Atomic orbitals is the wave functions of electrons in an atom.
The Shape of orbital can be determined from the angular part of
the wave function

Ylm ( ,  )
The Size of orbital and its spatial distribution can be determined
from the radial part of the wave function
Rn.l (r )
Shape of orbital
1
 1 2
Y00   
 4 
Y00 has spherical shape, hence it
is called “s orbital”.
 1
 3  2
Y10    cos 
 4 
1
 3  2  i
Y11    sin  e
 8 

“ p orbitals” are called for Y10, Y11, and Y1-1 since spectrum
lines resulted from these orbitals are the most intense
(principle)
 1
 5 
 3cos   1
2
Y20   
2

 16 
1
 15  2  i
Y21    cos  sin  e
 8 
1
 15  2 2 2i
Y2 2    sin  e
 32 

“ d orbitals” are called for Y20, Y21, Y2-1, Y22, and Y2-2 since
spectrum lines resulted from these orbitals are rather
diffuse.
 The levels of m can be determined only when atom is put
under magnetic field otherwise if they hold the same n
and l , they all have the same energy (degenerate).

Y10 orients in z direction and is called “pz”

however, Y11 , Y1-1 are not px and py

Y11  Y11 
sin  ei  ei 
sin  cos   Yp x

Y11  Y11 
sin  ei  ei 
sin  sin   Yp y
Similary for d orbitals , linear combinations of Y2+m give
dz2 , dx2-y2, dxy , dxz , dyz.
 Probability Distribution Functions

We use the wave functions to calculate the probability

distributions of the electrons.

The “position” of the electron is spread over space and is

not well defined.

We may use the radial wave function R(r) to calculate radial

probability distributions of the electron.

The probability of finding the electron in a differential

volume element dt is:

Dr. Sabry El-Taher 38

Probability Distribution Functions
The infinitesimal volume element in spherical polar coordinates
corresponding to dxdydz in Cartesian coordinates is:

Therefore,

At the moment, we’re only interested in the radial dependence.

The radial probability density is P(r) = r2|R(r)|2 and it depends only
on n and ℓ.

Dr. Sabry El-Taher 39

Size of orbitals
can be determined from the probability of finding electron in the
distance from nucleus or “radial distribution function”
  dV
2
Probability

  dxdydz
2

  r 2 sin  drd d
2

 2
  r dr  sin  d  d
2 2

 0

  r 2 dr   cos  
 
2
2
0

  r 2 dr  4
2

 4 r 2  dr
2

Probability  P (r )dr P(r)  radial distribution function

= r2|Rne(r)|2
R(r) and P(r) for the
lowest-lying states of
the hydrogen atom.

Dr. Sabry El-Taher 41

 Probability distribution

Charge distribution

Dr. Sabry El-Taher 42

s orbitals -  = 0
1s – no nodes
2s – 1 node
3s – 2 nodes

n -  - 1 radial nodes,
 Angular nodes ,
n – 1 total nodes

Dr. Sabry El-Taher 43

Copyright – Michael D. Fayer, 2007
p-orbitals presentation

d-orbitals presentation

Dr. Sabry El-Taher 44

 Quantization of Orbital Angular Momentum
It can be shown that the finiteness of the wave function on the z-axis
requires that the orbital angular momentum be quantized:

where

is called the orbital angular-momentum quantum number

or orbital quantum number.
Also, it can be shown that because of angular periodicity of the wave function,

the z-component of the orbital angular momentum must be quantized as well:

where

is called the orbital magnetic quantum number

or magnetic quantum number.

Dr. Sabry El-Taher 45

Orbital Angular Momentum Quantum Number ℓ
It’s associated with the R(r) and f(θ) parts of the wave function.
Energy levels are degenerate with respect to ℓ (the energy is
independent of ℓ).
ℓ= 0 1 2 3 4 5..
Letter = s p d f g h...

The letters s, p, d, and f are the first letters of “sharp”, “principal”,

“diffuse", and “fundamental”, respectively, used in the early days
of spectroscopy.
Atomic states are usually referred to by their values of n and ℓ.
A state with n = 2 and ℓ = 1 is called a 2p state.
Another widely used notation is
n 1 2 3 4 ···
Shell K L M N ···
Dr. Sabry El-Taher 46
Magnetic Quantum Number mℓ
The solution for g() specifies that mℓ
is an integer and is related to the z
component of L:

Example: ℓ = 2:

(see the Figure)

Only certain orientations of are

possible. This is called space
quantization.

And (except when ℓ = 0) we just

don’t know Lx and Ly!
Dr. Sabry El-Taher 47
Dr. Sabry El-Taher 48
s orbitals

 The surfaces include 90% of the total density.

 The density of shading represents the probability density.
 The white circles, one in the 2s and two in the 3s show the nodes
where the densities are zero.
Dr. Sabry El-Taher 49
 p-orbitals

 Note the nodal plane and the opposite signs of the wavefunction
on either side, so unlike s-electron, p-electrons are never found at
the nucleus.
 The p orbitals are labelled according to the axes along which the
lobes are directed.
Dr. Sabry El-Taher 50
d-orbitals

 Dark orange indicates +ve and light orange -ve.

 Note that the upper pair have lobes directed along the axes whereas
 in the lower three they are directed between the axes. This has
 fundamental importance in transition metal complexes.
Dr. Sabry El-Taher 51
 f-orbitals

Properties of the lanthanides (rare earths) determined by the f orbitals.

Dr. Sabry El-Taher 52
Magnetic Effects on Atomic Spectra:
The Zeeman Effect
In 1896, the Dutch physicist Pieter Zeeman Nucleus
showed that spectral lines emitted by atoms
in a magnetic field split into multiple energy
levels. It is called the Zeeman effect.
Consider the atom to behave like a small magnet.
Think of an electron as an orbiting circular current loop of I = dq / dt
around the nucleus. If the period is T = 2 r / v,

then I = -e/T = -e/(2 r / v) = -e v /(2 r).

The current loop has a magnetic moment:

e
 = IA = [-e v /(2 r)]  r2 = [-e/2m] mrv   L
2m
Where A is the area of the circle and L = mvr is the magnitude of the
orbital angular momentum.
Dr. Sabry El-Taher 53
 The Zeeman Effect 
e
L
2m

The potential energy due to the

magnetic field is:

If the magnetic field is in the z-direction, we only care about the

z-component of :

e e
z   Lz   (m l )   B m l
2m 2m
where B = eħ / 2m is called the: Bohr magneton.

Dr. Sabry El-Taher 54

 The Zeeman Effect
A magnetic field splits the mℓ levels. The potential energy is quantized
and now also depends on the magnetic quantum number mℓ.

When a magnetic field is applied, the 2p level of atomic hydrogen is

split into three different energy states with energy difference of
ΔE = B B Δmℓ.

mℓ Energy
1 E0 + μBB
0 E0
−1 E0 − μBB

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The Zeeman Effect

The transition from 2p to 1s,

splits by a magnetic field.

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The Zeeman Effect
An atomic beam of particles in the ℓ = 1 state pass through a
magnetic field along the z direction.

 B m (dB / dz )

The mℓ = +1 state will be deflected down, the mℓ = −1 state up,

and the mℓ = 0 state will be undeflected.
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 Spectral transition
and selection rules
For hydrogen, the energy level depends
on the principal quantum number n.
An electron can make a transition from a
state of any n value to any other.
But what about ℓ and mℓ quantum
numbers?
The change in electronic state results in
the emission or absorption of a photon.

When electron changes state, there will be a change in angular

momentum and in turns photon is released.

Not all transition between any two electronic states can occur.
Angular momentum must be conserved for the transition to be
possible called “allowed” transition, else called “forbidden” transition.
:Allowed transitions:
Electrons absorbing or emitting photons can change states when
Dℓ = ±1 and Dmℓ = 0, ±1
n is unrestricted because it doesn’t relate to angular momentum.
For this conservation to occur:
An electron in a d orbital (ℓ = 2) cannot make a transition into an s
orbital (ℓ = 0) because the photon cannot carry away enough
angular momentum.
An s electron cannot make a transition to another s orbital
because no angular momentum is produced for the photon.

Forbidden transitions:
Other transitions are possible but occur with smaller probabilities.
This is the selection rule for the electronic transition in atom.
Electron Spin
Pauli postulated in 1925 that an electron can exist in two distinct states and introduced
in a rather ad hoc manner a fourth quantum number to describe the two states.
Although with this he could explain the Stern-Gerlach experiment, no interpretation
was given to the fourth quantum number. Before long, two Dutch graduate
students, Uhlenbeck and Goudsmit, proposed that the electron might behave like a
spinning sphere of charge instead of a point particle and the spinning motion would
give an additional spin angular momentum S and spin magnetic moment s.
According to this proposal, the spin angular momentum, like the quantized
orbital angular momentum, is also quantized:
where the spin quantum number s = ½, and what the Stern-Gerlach experiment
measures is the z-component of the spin angular momentum
where the spin magnetic quantum number ms, the fourth quantum number introduced
by Pauli, has two values +½ and -½, corresponding to the two orientations, up and down,
respectively, of the spin angular momentum.

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Intrinsic Spin
In 1925, Samuel Goudsmit and George S
Uhlenbeck, in Holland proposed that:
the electron must have an intrinsic angular
momentum and therefore a magnetic moment.

In order to explain experimental data, Goudsmit

and Uhlenbeck proposed that:
the electron must have an intrinsic spin quantum
number s = ½.
ms = +½ called “α spin” or “spin up”
ms = -½ called “β spin” or “spin down”
Photon also has spin with ms = 1
Particles with half-integer ms are called “fermion”
Particles with full-integer ms are called “boson”
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 Intrinsic Spin
The spinning electron reacts similarly to
S
the orbiting electron in a magnetic field.

The magnetic spin quantum number ms has

only two values: ms = ±½

The electron’s spin will be either “up”

or “down” and can never be spinning
with its magnetic moment μs exactly
along the z axis.

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