Module 2 "Atomic physics and atomic structure"

Lecture 7 Quantum Mechanical treatment of One-electron atoms

Page 1

Objectives

In this lecture, we will apply the Schrodinger Equation to the simple system Hydrogen
and compare the outcome of the Quantum Theory with the experimental results obtained
from different experiments.

We will also get to know about the wavefunction and its use in developing the concept
of the structure of atoms.
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Why hydrogen?

One electron atom and the simplest bound system in nature

Referring to the adjacent figure -1, the proton (+ve Charge) is at the center and the
electron (-ve charge) is moving around
the center.

The attractive force between them is Z

Coloumbic in nature and the potential is

Ze 2 z
V = V ( x, y , z ) =
4 0 x + y + z
2 2 2

y
x Y
.Equation -1
X
Where Z is the charge of the nucleus,
Figure - 1
Z = 1 for hydrogen.

Since it is a two body problem, we convert it to one body problem by introducing

reduced mass

mM
=
m+M

Where m and M are the masses of the electron and proton, respectively.

So, the total energy of the system = kinetic energy + potential enrgy

1
( p x2 + p y2 + p z2 ) + V ( x, y, z ) = E . Equation -2
2

Here, px, py, and pz are the linear momenta and E is the total energy.
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For the quantum mechanical treatment, we will convert the classical dynamical
quantities (px, py, and pz ) to its corresponding quantum mechanical operators

px i , p y i , pz i
x y z

E i
t

Substituting in Equation 2, we get

2 2 2 2
2 + + 2
+ V ( x, y , z ) =
i . Equation -3
2 x y z
2
t

Here, we introduce the WAVEFUNTION to represent the electron.

= ( x, y, z , t ) . Equation -4

The wavefunction contains the information about the position and the time evolution of
the electronic motion. We will understand more about this later.

So operating equation -2, on the wavefuntion, = ( x, y, z , t ) ,

2 ( x, y , z , t ) ( x, y , z , t ) ( x, y , z , t ) ( x, y, z , t )
2 2 2

+ + + V ( x, y , z ) ( x, y , z , t ) =
i
2 x 2
y 2
z 2
t
2 2
+ V =i
2 t
. Equation -5

2 2 2
=
2
+ + is the Laplacian operator.
x 2 y 2 z 2

This Equation -5 is known as Time dependent Schrodinger Equation.

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Since the potential V ( x, y, z ) does not depend on time t, and we are interested to evaluate
the energy of the stationary (time independent) states, we can take this wavefunction as
the explicit dependence of time such as

( x, y , z , t ) =
( x, y, z ) eiEt /

Substituting this to Equation -5, we get

2 2
( x, y, z ) + V ( x, y, z ) =
E ( x, y, z ) . Equation -6
2

This is the Time Independent Schrodinger Equation.

Now we have to evaluate the stationary state energies ( E ) of the electron in this system
by solving this equation to explain the observed spectra of hydrogen.

Since the potential is spherically symmetric

Ze 2 Ze 2 Z
V ( x, y , z ) = = = V (r )
4 0 x + y + z
2 2 2 4 0 r

We can convert Equation -6 to its spherical polar

coordinate (Figure -2) form, z
r
2 2 y
( r , , ) + V ( r ) ( r , , ) =
E ( r , , )
2 x Y

. Equation -7

Radial distance r, Polar angle and X

Azimuthal angle Figure - 2

The form of the Laplacian operator in Spherical polar coordinates is

1 2 1 1 2
=2 r + 2 sin +
2 2
r r r r sin
2
r sin
2
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Using the separation of the variables, we can write the wavefunction as the product form
of the independent variables R ( r ) , ( ) , ( )

( r , , )= R ( r ) ( ) ( )

Substituting in equation 7,

2 1 2 R 1 R 1 2 R
+ + + V ( r ) R
= ER
2 r 2 r r 2 sin 2 2
r sin
r r 2 sin

Carrying out the partial differentiation,

2 2 R R R 2
+ + + V ( r ) R
= ER
2 r 2 r r r 2 sin r 2 sin 2 2
r sin

2 r 2
Multiplying the this equation by and rearranging we get,
R 2

1 2 R 1 1 2 2 r 2
r + sin + + 2 E V ( r ) =
0
R r r sin sin 2 2

Separating the radial ( R ( r ) ) and angular ( ( ) , ( ) ) part

1 d 2 dR 2 r 2 1 d d 1 d 2
r + E V ( r ) =
sin
R dr dr 2 sin d d sin 2 d 2

Note here that the partial derivative forms are converted to total derivative form. Now
each equation should be equal to a constant, lets take as .
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So, the radial part is

1 d 2 dR 2 r 2
r + 2 E V ( r ) =
R dr dr
. Equation -8
1 d 2 dR 2
r + 2 ( E V ( r )) 2 R =
0
r dr dr
2
r

And the angular part is

1 d d 1 d 2
sin +
=
sin d d sin 2 d 2
sin d 1 d 2
sin + sin 2
= . Equation -9
d d d 2

Now, separating the polar and the azimuthal part

sin d d 1 d 2
sin + sin 2
=
=
ml2 . Equation -10
d d d 2

Here, we have taken that both sides should be equal to a constant m2. Note that we have
three independent equations from equation 9 and 10.
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Now let us first consider the azimuthal part (Equation -10)

1 d 2
=
ml2
d 2

1 d 2
+ ml2 =0
d 2

The general solution of this equation may be written in the form

1
ml ( ) =eiml ... Equation -11
2
2

( ) ml ' ( ) d =
ml ml '
*
Which satisfies the orthonormality condition ml
0

As the eigen functions must be single valued, i.e., (0) = (2) which means

eiml 0 = eiml 2
formula 1 Cos (ml 2 ) + iSin(ml 2 )
And using Eulers=

This is satisfied only if ml = 0, 1, 2, ..

Therefore, acceptable solutions only exist when ml can only have certain integer values,
i.e. it is a quantum number. Thus, ml is called the magnetic quantum number in
spectroscopy because it plays role when atom interacts with magnetic fields.
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Now we will discuss the polar part in Equation 10

sin d d
sin + sin =
2
ml2
d d

Rearranging, we get

1 d d ( ) ml2
sin + 2 ( ) =
0 ... Equation -
sin d d sin
12

Let us introduce new variable = Cos , the Equation-12 becomes,

d 2 d ( ) ml2
(1 ) +
( ) =
0 ... Equation -13
d d 1 2

The Equation-13 has singularities at = 1 , which may be eliminated by having a

solution in the form of

= (1 2 ) s / 2 u

Then Equation-13 becomes

d 2u du s 2 2 ml2
(1 )
2
2 ( s + 1) + + u =
0
d 2 d 1 2

Which can be written as

d 2u du s 2 ml2
(1 )
2
2 ( s + 1) + s s +
2
u =0 ... Equation -14
d 2 d 1 2
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The last singular term in Equation-14 can be removed by taking s = ml 0, and then we
have

d 2u du
(1 2 ) 2 (ml + 1) + [ ml (ml + 1) ] u =
0 ... Equation -15
d 2
d

Which is a regular equation and hence its series solution may be written as

u = ar r ... Equation -16

r =0

Substituting in Equation-15, yields the recursion relation

(r + ml )(r + ml + 1)
ar + 2 = ar
(r + 1)(r + 2)

Requiring that the series be (Equation-16) be limited by a certain power r = q, i.e.

requiring that it be a polynomial of order q, we have to introduce the condition

a=
r +2 0, ar 0 which requires =(q + ml )(q + ml + 1)

Where q = 0, 1, 2, 3, .

Now we introduce l =q + ml =0,1, 2,3,..... (orbital quantum number) such that

l ml

= l (l + 1)
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Then Equation-12 becomes

1 d d ( ) ml2
sin +
l (l + 1) ( ) =
0 ... Equation -
sin d d sin 2
17

This is well known associated Legendre differential equation with its solution as
associated Legendre polynomials

Clml Pl ml ( ) ... Equation -18

l ,ml =

Where Clml is the normalization factor and Pl ml ( ) is the associated Legendre polynomial
defined by

d l + ml ( 2 1)l
Pl = (1 )
ml 2 ml / 2

d l + ml 2l l !
d ml
= (1 2 ) ml / 2 Pl ( )
d ml

Where Pl ( ) is the ordinary Legendre Polynomial. This expression holds for negative
values of ml also

(l + ml )! ml
Pl ml ( ) = (1) ml Pl ( )
(l ml )!

From this we can establish the range of variation of the azimuthal (magnetic) quantum
number ml = 0, 1, 2, 3, , l

The associated Legendre Polynomials satisfy the orthonormilization property

2 (l + ml )!
1

P ( ) Pl ml ( ) d = l ,l
ml
l
1
2l + 1 (l ml )!

2l + 1 (l ml )!
So, Clml =
2 (l + ml )!
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Then Equation-18 becomes

2l + 1 (l ml )! ml
l ,ml = Pl ( ) ... Equation -19
2 (l + ml )!

So, we have now two quantum numbers, namely, Orbital (l) and magnetic (ml)

l = 0, 1, 2, 3, ...
ml =l , l + 1, ..., 0, ..., l 1, l

Depending of the value of l and ml, some of the Associated Legendre polynomials are

P00 = 1

(1 cos )
1/ 2
P10= cos P11= 2

(1 cos ) cos
1/ 2
1 3cos 2
P20 = P21 = 2

P22 = 1 cos 2
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These functions are

1.5

1.0

0.5

0.5
45 90 135 180

in Deg
Now, we can have the total angular part, from Equation-11 and -19

Yl ml ( , ) =
l ,ml ( ) ml ( )
2l + 1 (l ml )! ml
= Pl (cos ) eiml
4 (l + ml )!
.Equation -20
Recap
In this lecture, we have learnt the quantum mechanical treatment of
hydrogen atom problem.

To do this, we have used the separation of variables method and in this

method we have written the total wavefunction as a product function of the
radial part and the angular part.

Since the coulomb interaction between the nucleus and the electron is
radially symmetric, we have solved the angular part separately.

While solving the angular part of the wavefunction, we have introduced two
quantum numbers namely, azimuthal or orbital quantum number l and
magnetic quantum number ml .
(****Check the symbol in the lecture*********)

In the next lecture we will solve the radial part of the wavefunction and
will construct the total wavefunction of the hydrogen atom. We will also
calculate the energy levels of the hydrogen atom and will compare it with
the observed spectrum.