QUANTUM MECHANICS II

H-ATOM # 1
04, September-2017

BITS PILANI HYDRABAD CAMPUS ASRARUL HAQUE

OUTLOOK

H-ATOM
 H-ATOM
Electron ( m1)
Z=1
m p  1.7 1027 kg r1 r1  r2  r
19
q  1.6 10 C R
Proton
me  9.11031 kg (m2)
r2
The electrostatic interaction potential between the electron and the point-like
nucleus is
q 2 Ze 2 Ze 2 e2
V (r )     2 Ry 1
4 0 r r r v0    c;  
me 137
1
T  V  Ebind c
2 v0 
137
me v02
T  13.6eV  Ebind 1Ry  13.6eV
2
Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM

q2
V  2 Ry  
4 0 a0
Electron ( m1)

q2
 a0   0.5nm r1 r1  r2  r
8 0 Ry
R
Proton
(m2)
2 a0 r2
  1016 s
v0

Hydrogen is the most abundant element in the universe.

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM
The Hamiltonian for Hydrogen atom is
p12 p22 e2 2 2
e 2
H     2r1   r22 
2m1 2m2 r1  r2 2m1 2m2 r1  r2

The TISE for H-atom reads: Electron ( m1)

H  (r1 , r2 )  E  (r1 , r2 ) r1 r1  r2  r
R
 2 2
e 2
 Proton
   2r1   r22    (r1 , r2 )  E  (r1 , r2 ) (1) (m2)
 2m1 2m2 r1  r2  r2

The question is how to solve (1) to find .

Can we apply separation of variable method to (1)?

Ans: No. Why?
Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM
e2
The term  can not admit separation of variable since
r1  r2

r1  r2  ( x1  x2 ) 2  ( y1  y2 ) 2  ( z1  z2 ) 2  .

However at the level of Schrodinger equation, we can have some

identification in terms of reduction of 2-body problem in a single body
problem.
Reduction of 2-particle problem in a single particle problem:

 (r1 , r2 )   ( R, r )
with
r  r1  r2 ( x, y, z )   ( x1  x2 ), ( y1  y2 ), ( z1  z2 ) 
m1r1  m2 r2
R  ( X ,Y , Z ) 
m1  m2
Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM
The Schrodinger equation reads:

 2
 2 2 2  2
 2  2  2 
  2  2  2   2  2  2    ( x1 , y1 , z1 ; x2 , y2 , z2 )
 2m1  x1 y1 z1  2m2  x2 y2 z2  
e2
  ( x1 , y1 , z1 ; x2 , y2 , z2 )
( x1  x2 )  ( y1  y2 )  ( z1  z2 )
2 2 2

 E  ( x1 , y1 , z1 ; x2 , y2 , z2 ) (2)

Now:
 X  x  m1  
   
x1 x1 X x1 x M X x

 X  x  m2  
   
x2 x2 X x2 x M X x
Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM
Therefore:
2 m12  2 2m1   2
 2   2
x1
2
M X 2
M X x x
 m22  2 2m2   2
   2
x2
2
M X
2 2
M X x x

Now:
2
2 2
2 2
 m12  2 2m1   2 
    M 2 X 2  M X x  x 2 
2m1 x1 2m2 x2
2 2
2m1  
2
 m22  2 2m2   2 
    2
2m2  M X
2 2
M X x x 

2
2 2
2
= 
2 M X 2
2  x 2
Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM
Similarly:

2
2 2
2 2
2 2
2
   
2m1 y1 2m2 y2
2 2
2M Y 2
2  y 2

2
2 2
2 2
2 2
2
   
2m1 z1 2m2 z2
2 2
2M Z 2
2  z 2

Therefore:

 2
 2 2 2  2
 2 2  2 
  2  2  2   2  2  2    ( X , Y , Z ; x, y , z )
 2M  X Y Z  2  x y z  
e2
  ( X , Y , Z ; x, y, z )  E  ( X , Y , Z ; x, y, z ) (3)
x2  y 2  z 2
Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM
Now we can apply separation of variable method. Let

 ( R, r )   ( R) (r ).
We have:
 2
  2

  R  ER     
2
 r  V (r )  E    0;  E   ER  E 
2

 2M   2 
 m1m2 
 M  m1  m2 ,   , E   ER  E 
 m1  m2 
Thus:
2
  2R ( R)  ER ( R) (4)
2M

 2
e 2

  2  r  r  (r )  E (r )
2
(5)
 
Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM
2
  2R ( R)  ER ( R) (4)
2M

Equation (4) represents the Schrodinger equation for a free particle of mass
M and will have solutions

 ( R)  Aeik .R
and 2
K2
ER  .
2M
This solution correspond to the uniform motion of CM with ER being kinetic
energy associated with such motion. That is, the solution represents the
motion of the entire hydrogen atom.

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM

 2
e 2
  m1m2 m1m2 
  2  r  r  (r )  E (r )     m1 
2
(5)
   m1  m2 m2 

Equation (5) corresponds to the internal relative motion of electron and

proton, It represents SE for a single particle of mass  moving in the
potential in the potential V(r).

It is the solution of the equation (5) that would provide the energy levels and
the wave functions of the hydrogen atom.

Asrarul Haque QUANTUM MECHANICS – II 2017

 QUANTUM MECHANICS II

H-ATOM # 2+3
12, September-2017

BITS PILANI HYDRABAD CAMPUS ASRARUL HAQUE

In order to find wave functions and energies of H-atom, we need to solve
the following equation:

 2
e 2

  2  r  r  (r )  E (r ).
2

 

 (r )  ? En  ?
 H-ATOM
Now:
 2
e 2

  2  r  r  (r )  E (r )
2

 

We know:
1   2   1  1     1  2

r  2  r  2  sin    sin    2
2
2
r r  r  r    sin   
1   2   1 L2
 2 r  2 2
r r  r  r

 1     1  2

L    sin   2
2 2
2
 sin      sin   
Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM
Here:

 2
e 2

  2   r  r  (r )  E (r )
2

 

 2 1   2   1 e 2

  r  L   (r , ,  )  E (r ,  ,  )
2

 2 r r  r  2 r
2 2
r

Let:  (r )   (r ,  ,  )  R(r )Ylm ( ,  )

L2 (r , ,  )  L2 R(r )Ylm ( ,  )  R(r ) L2Ylm ( ,  )  R(r ) 2l (l  1)Ylm ( ,  )

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM
 2
1   2   2
e2 
  2 r 2 r  r r   2 r 2 l (l  1)  r  R(r )  ER(r )
   

  2 2  l (l  1) 2  e 2 2  
 2    2  2 E  R(r )  0
 r r r 2
r r 

We wish to solve the SE for bound states which have energy E < 0.
1
 8E   2 2 e2 1 e2 
Let:        r and   

2

2
 2E
Then,

 2  2 2   2 2 e2  2 
  2    2 l (l  1)  2  2 E  R(  )  0
        
Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM

 2  2 2   2 2 e2  2 
  2    2 l (l  1)  2  2 E  R(  )  0
        

 2 2  1 2 e2 1 2 E 1 
 2   2 l (l  1)  2  2 2
R(  )  0
       

 2 2  1  1  2 e2 1 e2  
 2   2 l (l  1)    R(  )  0    2  
      4
  2E 
 2E  2
1   2 8E  
 2     
8 E  
2
 4 

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM
Asymptotic Behaviour
   : (Large  )

For large 

 2 2  1  1 2 R 1
  2      2 l (l  1)    4  R(  )  0   2  4 R  0
 
Solutions are:
  2
e
R(  ) ~  
e 2
 

We must have R  0 as   . Only R(  ) ~ e 2
is acceptable.

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM
Asymptotic Behaviour
  0 : ( Small  )

For small 

 2 2  1  1  2 2  1 
  2      2 l (l  1)    4  R(  )  0    2      2 l (l  1)  R(  )  0
   

Let: R(  ) ~ 


 (  1)  2  l (l  1)  0 
 l

 R(  ) ~   l 1
   l , l  1 


Only R(  ) ~  l is acceptable.
Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM
We can now assume:


R(  )   l e 2 G (  ).

 2 2  1  1
  2      2 l (l  1)    4  R(  )  0
 



R(  )   l e G (  )
2

 2G G
 2   2l  2        l  1 G  0 H.W.
 

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM
We have:
 2G G
 2   2l  2        l  1 G  0
 

Let: G (  )   a    a0  a1   a2  2  .....


d
 G   [a1  2a2   3a3  2 .....]  [2a2  6a3  .....]
d

(2l  2   )G  (2l  2   )[a1  2a2   3a3  2 .....]

(  l  1)G  (  l  1)[a0  a1   a2  2 .....]

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM
Now:

 2G G
 2   2l  2        l  1 G  0
 

 [2a2  6a3  .....]  (2l  2   )[a1  2a2   3a3  2 .....]

    l  1  a0  a1   a2  2   0

  0    l  1 a0  (2l  2)a1     2a2  a1  2a2 (2l  2)  a1 (  l  1) 

  2  6a3  a2 (  l  1)  3a3 (2l  2)  2a2   0

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM
Now:

  0    l  1 a0  (2l  2)a1     2a2  a1  2a2 (2l  2)  a1 (  l  1) 

  2  6a3  a2 (  l  1)  3a3 (2l  2)  2a2   0

    l  1 a0  (2l  2)a1  0

a1 (  l  2)  a2 (4l  6)  0

a2 (  l  3)  a3 (6l  12)  0

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 H-ATOM

Recursion Relation for coefficients reads:     l  1 a0  (2l  2)a1  0

a1 (  l  2)  a2 (4l  6)  0
(  l  1   ) a2 (  l  3)  a3 (6l  12)  0
a 1  a
(  1)(  2l  2)

For large   

a 1 1

a 

This behavior shows that

1

  
b 1 (  1)! 1
G(  ) ~ e e 

  b  ;

 
 0  !  0 b 1 
!
Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM

 R(  )   l e   /2e   e  /2

That is inconsistent with the behavior that wave function is normalizable.

The only way to avoid this is to require that series must terminate so
that G (  ) goes as some power of  rather than as e .


Series will terminate if

1
  e4  2
  l 1   0    2 
   l 1  n
 2 E 
 e4
or , En  
2n 2 2

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM
Bohr Radius:

2 2
a0    0.55 1010 m
 e2 m1e 2

Energy:

 e4 e2 e2 13.6
En   2 2
 2
  2   2 eV
2n 2n a0 n
2n 2
 e2

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 H-ATOM

 2G G
 2   2l  2        l  1 G  0
 

This is associated Laguarre equation. The solution G (  ) are given by

G (  )   L2nll1 (  )

 
 
 Rnl (  )   l e 2 G (  )    l e 2 L2nll1 (  )

 
2 n[( n  l )!]3

 d  Rnl (  )  
2
   2l  
L2nll1 (  ) 
2 2 2
d e
0 0
(n  l  1)!

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM
The normalized wave function for Hydrogen Atom:

 nlm (r , ,  )  Rnl (r )Ylm ( ,  )

Where:
1
3/ 2 l
 2   2r  2l 1 2r
r
 (n  l  1)!  2 
Rnl (r )      3 
e a0
  Ln l ( )
 na0   2n((n  l )!)   na0  na0

1
 (2l  1)(l  m)!  im m 2
Ylm ( ,  )    e Pl (cos  ),
 4 (l  m)! 
2
a0   0.529 1010 m.
 e2
Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM
The Normalization condition:

 nlm
     nlm
   sin  d d dr  1
2 3 2 2
( r , , ) d r ( r , , ) r

  Rnl (r )Ylm ( ,  ) r 2 sin  d d dr  1

2

Moreover:

 Rnl dr  1
2 2
r
0

2 

 d  d Y ( ,  ) sin  d d  1
2
lm
0 0

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM
The eigen-energies for Hydrogen Atom:

1   e4  13.6eV
En   2  2   
n 2  n2
13.6eV
H nlm (r , ,  )  En nlm (r ,  ,  )   2
 nlm (r , ,  )
n
L2 nlm (r , ,  )  2
l (l  1) nlm (r ,  ,  )

Lz nlm (r , ,  )  m  nlm (r ,  ,  )

Principal Quantum No.: n  1, 2,..., .

Azimuthal Quantum No.: l  0,1, 2,..., n  1.

Magnetic Quantum No.: m  l , l  1,..., 1, 0, 1,..., l  1, l.

Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM
Degeneracy
What are the total number of states with energy En ?

For a given energy level (specified by n), there are n possible

values of l ,

and for each l there are 2l  1 possible values of m.

So the total number of states for a given n is :

n 1
1 + 3 + 5 + …+ (2n-1) =    2
(2l 1) n
l 0

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM

L11 (  ) 1  nlm (r , ,  )  Rnl (r )Ylm ( ,  )

L12 (  ) 4  2 
3/2
1
r


L ( )
3 R10  2   e a0
2 18  6   3 2  a0 
3/2
2  1   r 
r
1 
Y00 R21     e
2 a0
4 3 0 
2 a  2a0 
1/ 2
1 3 
3/2
 1   
r
r 
Y11   sin  e  i
R20  2    1   e 2 a0
2  2   2a0   2a0 
1/ 2
1 3 
Y10   cos 
2 

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM  nlm (r ,  ,  )  Rnl (r )Ylm ( ,  )
A few Hydrogen atom wave functions for quantum numbers n, l, m:
1/2
 1 
r

 100  R10Y00   3  e a0

  a0 
1/2
 1   r 
r

 200  R20Y00   3  2  e
2 a0

 32 a0   a0 
1/2
 1   r 
r

 210  R21Y10   3   e
2 a0
cos 
 32 a0   a0 
1/2
 1   r 
r

 211  R21Y11   3   e
2 a0
sin  e  i
 64 a0   a0 
Asrarul Haque QUANTUM MECHANICS – II 2017
 SPECTROSCOPIC NOTATION

The states with s p d f

E
0
l  0,1, 2,3, 4... -13.6eV/16 n=4
are referred as -13.6eV/9 n=3
s, p, d , f ... states.
-13.6eV/4 n=2

State  n  1, l  0   1s
State  n  2, l  0  = 2s
State  n  2, l  1 = 2 p
-13.6eV n=1
Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM
Probability Density

The probability density for the 1s state (Ground State) is

2  1  2r ao
ψ100   3 e
 πao 

The radial probability density function P(r) is the probability per

unit radial length of finding the electron in a spherical shell of
radius r and thickness dr.

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM
Probability Density

A spherical shell of radius r and thickness dr has a volume of

4πr2 dr.

The radial probability function is

P(r) = 4πr2 |ψ|2

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM
Probability Density
The radial probability density function for the hydrogen atom
in its ground state is

 4r 2  2r
P (r )   3  e ao

 ao 

The peak indicates the most probable location.

The peak occurs at the Bohr radius.

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM

n = 1, l = 0

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM

1. Assume that the nuclear diameter for H is 2 × 10-15 m. Using

this assumption, what is the total probability of finding the
electron in the nucleus if it occupies the 2s orbital.
3/ 2
1  1   r   r / 2 a0
 2 s (r )   200  r     2 e
32  a0   a0 

The total probability is given by

2  2
1  1   r   r / a0
rnucleus

P    200  d  sin  d 
2
d r
3
  r 2
2
 e dr
32  a0  0 0 0  a0 

Asrarul Haque QUANTUM MECHANICS – II 2017

 H-ATOM

Because rnucleus  a0 , we can evaluate the integrand by

assuming that 2  r / a0 2 e  r / a is constant over the interval
0

0  r  rnucleus .
2  2
1 1 2 r   r / a0
rnucleus

P    d  sin d 0 r  2  a0  e dr

32  a0  0 0

1  1 
3
  rnucleus 
2
 rnucleus
P   4  2   e
 rnucleus / a0
  r 2 dr
32  a0   a0   0

1 1  3
rnucleus   rnucleus / a0  4 3
2

    2   e  rnucleus
32  a0   a0   3

Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM

1 1 3
 rnucleus   rnucleus / a0  nucleus 2
2 r

P   4  2   e   r dr
32  a0   a0   0

1 1 
3
 rnucleus   rnucleus / a0  4 3
2

    2   e  rnucleus
32  a0   a0   3


Because: 2   rnucleus / a0   2 and e  rnucleus / a0  1.  rnucleus  a0 

3
1  rnucleus  15
P    9.0 10
6  a0 

Because this probability is vanishingly small, even though the wave

function has its maximum amplitude at the nucleus, the probability of
finding the electron in the nucleus is essentially zero.
Asrarul Haque QUANTUM MECHANICS – II 2017
 STABLITY OF H-ATOM
r  0.5 1010 m, v  106 m / s
mv 2 e2 v

r 4 0 r 2 -e
v2 e2 2
r
a   10 22
ms
r 4 0 mr 2
+e
(ea) 2
Power radiated: P   1011
eV / s
6 0 c 3

Electron would loose its energy very rapidly (~1012 s ) and drop
into the nucleus.
Electrons move not in circular orbits, but in 'fuzzy‘ orbits. Actually, we cannot tell
how it moves, but only can say what is the probability of finding it at some
distance from the nucleus.

Only certain “orbits” or shells of electron probability densities are allowed.

Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM
3/ 2
1
r

R10 2  e a0

 a0 
3/ 2
 1     2 a0
r
r
R20 2   1  e
 0
2 a  2a0 
3/ 2
2  1   r   2 a0
r
R21    e
3  2a0   2a0 

1
Y00 4
1/ 2
1 3 
Y11   sin  e  i
2  2 
1/ 2
Y10 1 3 
  cos 
2 
Asrarul Haque QUANTUM MECHANICS – II 2017
 H-ATOM

A few Hydrogen atom wave functions for quantum numbers n, l, m:

1/2
 1 
r

 100  R10Y00   3  e a0

  a0 

H-ATOM
H-ATOM

1/2
 1   r   2 a0
r

 200  R20Y00   3  2  e
 32 a0   a0 

1/2
 1   r 
r

 210  R21Y10   3   e
2 a0
cos 
 32 a0   a0 
1/2
 1   r 
r

 211  R21Y11   3   e
2 a0
sin  e  i
 64 a0   a0 
Asrarul Haque QUANTUM MECHANICS – II 2017