6.

Atomic Structure
6.1. The Hydrogen Atom

Hydrogen-atom Spectra
 The radiation emitted by excited atoms produces line spectra.

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 Atomic structure

Experimental result

 1 1 
  R  2  2  where : n1  1, 2,3,.. n2  2,3, 4,... and n2  n1.
 n1 n2 

Rydberg constant, R = 3.2880  1015 s-1

Using photon energy,
 1 1 
 ( J )  2.1787  10 18
 2 2
 n1 n2 

 Hydrogen atoms can change their energies only by the definite

amounts

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 Atomic structure

The Bohr Theory of the Hydrogen Atom

Basis for the Bohr description of the hydrogen atom:

 The electron moves about the nucleus in a circular orbit.
 Only orbits in which the electron has an angular momentum
that is an integral multiple of h/2 are allowed.
nh
meur 
2
 The electron does not radiate energy when it is in an allowed
orbit, but it can gain or lose energy by moving from one orbit to
another.

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 Atomic structure
 The force of attraction between a nuclear charge of +e and the
electron charge of -e is given by
e2 1
Force 
4 0 r 2
o = vacuum permittivity = 8.854 19  10-12 C2 N-1 m-2

 In a circular orbit, the electron is accelerated toward the nucleus

by a force equal to:
meu 2
Force 
r
Equating the two yields,

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 Atomic structure

Radii of the first Bohr orbit ao, is:

 The model can be extended to “hydrogen-like” atoms.

 General expression for the radii of Bohr orbits:
n2
r  ao
Z
Allowed Energies
The total energy of the electron – proton system is:

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 Atomic structure

Substitution for the expressions of u and r yields

 The change in energy when an atom or molecule in an excited

state relax back to a lower state through emission of
electromagnetic radiation is:

 Assuming the energy given off is photon energy, E = h,

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 Atomic structure

Let

which is equivalent to 109737 cm-1.

 It is very close to the experimental value of 3.2880 × 1015 s-1 (or
109677.6 cm-1).

6.2. Schrödinger Equation of the Hydrogen Atom

 The time-independent Schrödinger equation for H-like (one-
electron) systems:

8 2
 ze 2
2 ( r , , )  2 ( E  ) ( r . , )  0
h 4 o r
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 Atomic structure

Separation of variables:

 ( r , , )  R( r ) ( , )  R( r )Yl m( , )

R(r) - the radial wave function involving only r

(,) – the angular wave function involving  and 

 Using the polar coordinate, the Schrödinger equation becomes

2 1  1 2

H (r ) R(r )    ( , )
H (r ) R(r )  ( ,  )   R(r ) ( ,  )  0 R(r )  ( , ) 

where
2
   2 ze2 r 8 2  Er 2
H (r )  r2  2r  
r 2
r  oh 2
h2
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 Atomic structure

 1     1 2
 2
 sin    sin 2   2
sin     
The equation holds only if each side of the equation is equal to a
constant 𝑙 𝑙 + 1 .
Accordingly, after rearrangement,

H (r ) R(r )  l  l 1 R(r )

 2
( ,  )
  l  l 1 ( , )

Substitute for H ( r ) , the equation for the radial component becomes,

ℎ2 𝑑 2 𝑑𝑅 ℎ2𝑙 𝑙 + 1
− 2 2 𝑟 + 2 2
+ 𝑉(r) − 𝐸 𝑅(r) = 0
8𝜋 𝜇𝑟 𝑑𝑟 𝑑𝑟 8𝜋 𝜇𝑟
e2
where V( r )   4 r
o

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 Atomic structure

6.3. Hydrogen Wave Functions

6.3.1 The Angular Wave Function

Solution
 Same as particle on a sphere
1
  2l  1  l  m ! m
 l, m ( , )   4
2
 im
 Pl (cos  )e
  l  m !

 l specifies the total angular momentum and m specifies the z-

component of the angular momentum.

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 Atomic structure

6.3.2. The Radial Wave Function

Solution
1
 2 z 3  n l 1! 2 

Rn, l (r )    2  l 2l  1(  )
 e Ln  l
 o  2n  n  l ! 
3
na
 
2 zr

nao
0 l  n-1 and n = 1,2,3…
a !   a (a  b)  a b 1
a (a 1)(a b)  a b  2 
L a  n  l ( )   
b  2l  1 a b
 ,...
(a b)!  1! 2! 

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 Atomic structure

Example
Determine the solution for the radial distribution function when n = 1
and l = 0.
Solution
1
 3
2 z  (1 0 1)!  2  2 zr  
0

2a0  2 zr  01
R1, 0     e  L1 0

 
a0  2 (1 0)! 3  

 a 
 o 

0 1 1!
 11
L10 (1  1)!  1


Therefore
3 zr 3
 
 z  2 ao  z  2 
R1, 0  2  e  2  e 2
 ao   ao 
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 Atomic structure

6.3.3. Total wavefunction for hydrogen-like atoms

 n,l ,m ( , )  Rn,l ( r ) l ,m ( ) m ( )

Examples
3 1 3

 Z  2  1 
2
1  Z   2
2 2
 100  R10 00( , )  2  e      e
 ao   4    ao 
3 1 3
1 Z 2 

1   2     Z 
2 

2    e 2   
2
 200  R20 00( , )  1    e
2

 4  4 2  ao 
82  o 
a

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 Atomic structure

6.4. Energy Eigenvalues of H-Spectrum

6.4.1. Derivation of the Rydberg Formula
 The total energy is the sum of the radial kinetic energy, the angular
kinetic energy and the potential energy.
 The total energy of the electron – proton system is therefore
𝑍2He4
𝐸n = − 2 2 2 n = 1, 2, 3, …
8o ℎ 𝑛
Where, Z = nuclear charge
Note: Since mp >> me,
1 1 𝑚e𝑚p
= + = = 𝑚e and ZH = 1
𝑚e 𝑚p 𝑚e+𝑚p

 It is the same as Bohr’s energy.

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 Atomic structure

 The energy given off during relaxation is:

He4 1 1
∆𝐸n = 2 2 2 − 2
8o ℎ 𝑛1 𝑛2
 It is similar with the experimentally based Rydberg formula where
H is replaced by me.

 In terms of wave number,

1 𝑚 e𝑒 4 1 1 1 1
= − 2 =RH + 2
 8o cℎ 𝑛1
2 3 2 𝑛2 𝑛1 2 𝑛2
𝑚 e𝑒 4
Where, = RH
8o2ch3
RH = The Rydberg constant = 109737 cm-1 (Theoretical Value)
= 109677.6 cm-1 (Experimental value)
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 Atomic structure

 The ground state energy of a hydrogen atom is E1= -hcRH = 2.179

× 10-18J = -13.60 eV
 The energy that must be supplied to ionize the atom is:
EI = hcRH = 13.60 eV
 The probability of finding an electron at a given radius is:
P( r ) dr    n2,l ,m d  R2 r 2
E.g. For a 1s state, the probability of finding the electron between r
and r + dr is:
3
4 2  2 r ao  z  2  2 zr ao
P 5r e dr  4   r e
ao  ao 
rmax is at dP/dr = 0.
Therefore: rmax = a0/z
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 Atomic structure

 In the quantum mechanical model, the electron is not restricted to

the sharply defined orbits of Bohr,
 The general expression for the mean radius of an orbital with
quantum numbers l and n is:

 1  l  l  1   ao
rn,l  n 1  1 
2
2 
 2  n   Z
 For a given principal quantum number, the mean radius decreases
as 1 increases
 E.g. The average distance of an electron from the nucleus is less
when it is in a 2p orbital than when it is in a 2s orbital.

 Each hydrogenic atomic orbital is defined by three quantum

numbers, designated n, l and ml.
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 Atomic structure

 An electron described by the wavefunction 100 is said to occupy

the orbital with n = 1, l = 0, and. ml = 0.
 The quantum number n determines the energy of the electron.
 Quantum numbers, l and ml specify the angular momentum of the
electron around the nucleus.
 An electron in an orbital with quantum number l has an angular
momentum of magnitude:
h
L  l (l  1) with l = 0, 1, 2..., n-1
2

 An electron in an orbital with quantum number ml , has a z-

component of angular momentum
h with m = 0, 1, 2, ...l
ml l
2

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 Atomic structure

 The state of an electron in a hydrogenic atom, is defined by the

values of four quantum numbers, namely n, l, ml and s (either +½
or -½).
6.4.2. The Spectral Selection Rule
 A spectrum does not arise from the transition of an electron from
any initial orbital to any other orbital.
Reason:
 A photon has an intrinsic spin angular momentum corresponding to
s = 1.
 The change in angular momentum of the electron must compensate
for the angular momentum carried away by the photon.
 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.

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 Atomic structure

 An s electron cannot make a transition to another s orbital, because

there would then be no change in the electron's angular momentum
to make up for the angular momentum carried away by the photon
 A selection rule is a statement about which transitions are allowed.
 They are derived (for atoms) by identifying the transitions that
conserve angular momentum when a photon is emitted or
absorbed.
 The selection rules for hydrogenic atoms are:
l =  1 and ml = 0,  1
 The principal quantum number n can change by any amount
6.5. Atomic Spectra in Magnetic Field
 The motion of an electric charge around a closed loop produces a
magnetic dipole, m.
𝑒
𝑚= − 𝐿 where L = angular momentum
2𝑚e
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 Atomic structure

 In the presence of a magnetic field, the energy of an electron of a

hydrogen atom is:
me e4
E   2 2 2   B ml Bz
8 o h n
Where
|e|h
B   Bohr magneton  9.2740 1024 JT 1
4me
T = tesla = NA-1m-1
Bz = magnetic field strength along the z- axis

Note: In the presence of a magnetic field the energy is a function of

n and ml.

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 Atomic structure

 A state with given values of n and l will split into 2l + 1 levels (

differing in ml) by an external magnetic field.
Example:
For 1s state, l = 0, 2l + 1 = 1
 Hence no energy splitting in a magnetic field
For 2p state, l = 1, 2l + 1 = 3
 Hence the energy splits into three states when external magnetic
field is applied

Zeeman Effect: The splitting of energy levels due to external

magnetic field

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 Atomic structure

+1
2p 0
-1

1s

spectrum

The splitting of the 2p state in a magnetic field

6.6. The Electron Spin

 It is the intrinsic angular momentum of the electron due to its
motion about its own axis.
 s = spin quantum number, s = ½
 ms = spin magnetic quantum number – for the projection on the z-
axis
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 Atomic structure

 The value is restricted to 2s + 1= 2 different orientations.

 The spin angular momentum for an electron is given by:
h
S s(s  1
2

Spin – Orbit Coupling: It is the interaction of the spin magnetic

moment with the magnetic field arising from the orbital angular
momentum
Total angular momentum: The sum of orbital angular momentum
and spin angular momentum

Stern-Gerlach Experiment:
 A beam of silver atoms (4d105s1) was passed through an
inhomogeneous magnetic field.
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 Atomic structure
 Classically, since the orientation of the angular momentum can take any
value, a broad band of atoms is expected to emerge from the region
where the magnetic field acts.
 Quantum-mechanically, however, a state with a given value of l will be
restricted to 2l + 1 discrete orientations, and so such a system will be
split into 2/ + 1 components
Observation: The beam of silver atoms splits into only two parts.
 This corresponds to 2l + 1 = 2 where l = ½.

6.7. Pauli Exclusion Principle

 No more than two electrons may occupy any given orbital, and if two do
occupy one orbital, then their spins must be paired.

 The exclusion principle is the key to the structure of complex atoms, to

chemical periodicity, and to molecular structure.
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 Atomic structure
 The Pauli exclusion principle applies to any pair of identical fermions
(particles with half integral spin).
 Thus it applies to protons, neutrons, 13C nuclei (all of which have spin
½).
 It does not apply to identical bosons (particles with integral spin), which
include photons (spin 1), 12C nuclei (spin 0).
6.8. Schrödinger equation of many electron atom
The Schrödinger equation for a many-electron atom is highly complicated.
Reason: The electrons interact with one another.
The wave function is described by (r1, r2,..) where ri is the distance from
the nucleus to the electron i.

It is approximated as:  𝑟1, 𝑟2, … =  𝑟1  𝑟2 …

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 Atomic structure

Example: For He atom the Schrödinger equation is described by:

ħ2 2 ħ2 ħ2
𝛻 − 𝛻12 − 𝛻22  𝑅, 𝑟1, 𝑟2
2𝑀 2𝑚e 2𝑚e
2𝑒2 2𝑒2 𝑒2
+ − − +  R, r1, r2
4𝜋𝜀o 𝑅 − 𝑟1 4𝜋𝜀o 𝑅 − 𝑟2 4𝜋𝜀o 𝑟1 − 𝑟2
= 𝐸 𝑅, 𝑟1, 𝑟2
 R is the position of the helium nucleus,
 r 1 and r2 are the positions of the two electrons
 M is the mass of the nucleus, and me is the electronic mass
 𝛻2 is the Laplacian operator with respect to the position of the
nucleus
 𝛻12 and 𝛻22 are the Laplacian operators with respect to the
positions of the two electron
27