Recap of Toy Problems & Introducing H-Atom

Lecture 9
Recap of Toy problems & Introducing H-atom

Recap:
Particle in box case – Zero-point energy is finite since position has to be definite, so Energy
cannot be simultaneously definite (zero).
Angular Momentum :  can be indefinite, Energy can be definite (zero).
Armed with this, we can think about the QM of a particle of mass m constrained to be a sphere.
Now we have to think of,
Lˆ 2  Lˆ x 2  Lˆ y 2  LˆZ 2
1 ˆ2
Hˆ  L ; I = moment of inertia
2I
Clearly, quantum state now   ,  

Z
Also, bound motion
so we expect E to
 R be quantized and two
quantum numbers
 y due to symmetry
 :  ,   we only need to
x  consider 0 to 
 : 0,2
One quantum number is associated with  : ml => precession about z-axis.

What is the other one? xy plane rotation (θ), for that,
 1     1 2 
Lˆ    
2
2
  sin  
 sin      sin 2   2 

L2Z part.
(This is written in spherical polar coordinates )

Thus the Schrödinger equation that we have to solve is :
 2  1     1  
  sin   2   ,    E   ,  
2I  sin      sin   2 
This is a partial differential equation. The solutions are known,
  ,    Ylm  ,  
l
; Spherical Harmonics.
Ylml  ,    N lml Pl ml  cos   eiml


Polynomial in cos 
Normalization our LZ eigenfunctions
Constant.
Now, l is the other quantum number apart from ml .

What one obtains is that the spherical harmonics satisfy :
 2
l  l  1 
Hˆ Yl ml  ,      Yl ml  ,  
 2I 
Lˆ Yl ml  ,     2l  l  1  Yl ml  ,  
2
LˆZ Yl ml  ,     ml  Yl ml  ,  
 They are eigenfuctions of Hˆ , Lˆ and Lˆ .

2
  E  0,  LZ  0 and Square of Ang. Mom. is known with certainty.
* But Ylml are not eignfunctions of Lˆ x and Lˆ y .

These restrictions on quantum
Also, l  0,1,2,.... (integer) numbers have been logically
discussed. Restriction on ml arise to
But ml  0, 1, 2,...., l i.e, ml  l . satisfy the condition of simultaneous
eigenfunction of Hˆ , Lˆ and Lˆ
2
Now, note that Energy does not depend on ml !
2
El ml  l  l  1 ; independent of ml .
2I
Why
?
In fact, since ml  0, 1, 2,...., l there is a degeneracy of  2l  1 .
2
For e.g. E10  E1,1  E1,1  (3 fold deg.).
I
Reason that Energy is independent of ml is because our choice of Z -axis is arbitrary. We

could have chosen Lx or L y to describe our projections and the system does not care about
our convention / choice. Thus, Energy cannot depend on ml !
Since Yl ml is an eigenfn. of Hˆ , Lˆ and LˆZ this means we can determine there values
2
simultaneously with arbitrary precision. At the same time we cannot observe the precise values
of Lˆ x or Lˆ y !
Again, this has to do with uncertainity principle. Since LZ  0     . This, in turn,
means that the angular mom. vector can lie anywhere on a cone!
Completely Uncertain
Figures above.
Let us take a simple example to illustrate the concept:
Suppose, l  1  ml  0, 1
Clearly,   Y10  ,   , Y1,1  ,   , Y1,1  ,  
N10 P10  cos   N1,1 P11  cos   l i N1,1 P1,1  cos   e i
 2
Also, H Y1,0 }  ,      Y1,0 }  ,  
ˆ
1
 I  1
Lˆ Y1,0 }  ,    2 Y1,0 }  ,  
2
2
and
1 1
But, LˆZ Y10  ,    0.Y10  ,  
LˆZ Y1,1  ,       Y1,1  ,  

2
Since, L̂ has eigenvalue 2 2 , the magnitude,
L 2 ; Since L > max. value of LZ

(projection)
 L and LZ cannot in same direction!
L2x  L2y  L2Z  L2  2 2
..
L2x  L2y  2
* Projected Motion in x-y plane

is circular with Radius .
Classically we can interpret this as ang. mom. vector precessing about Z -axis.
Now, for any 2-particle system undergoing rotational motion,
Center of mass
m1r1  m2r2
moment of inertia, I   r2 ; r  r1  r2
m1m2
and  ; reduced mass
m1  m2
 Think of a particle of mass  on a sphere of radius r. !
The C.M. is associated with translational motion of a body of mass  m1  m2  .
* Thus, what we have just discussed can be applied to diatomic molecules and the
Hydrogen atom.
Now, let us discuss the Hydrogen atom. Hydrogen atom is an exactly solvable problem in
Quantum Mechanics. The solutions of H atoms are the basis for us to solve many electron
atoms and molecules.
We now have to deal with electronic motion which is much faster as compared to the nuclear.
Also, the H-atom spectrum was one of the prime motivation for Quant. Mech. From the point of
view of chemistry, the H-atoms (the lightest ones around in a molecule) are crucial in chemical
reactions—including our vision process: The initial process of our vision is triggered by a proton
motion in about 6 fs timescale !!
The emission spectrum of H, was noted as early as 1885 (by Balmer), 1890 (Rydberg) : Long
before QM (~1925) !
Discrete spectrum.
Bohr, introduced the concept of quantization, Energy in terms of a integer.
(Rutherford, before that, argued the ‘planetary model’)
Problems with classical

Interpretation.
Bohr : Certain orbits stable.
Why QM provides the answer.

?
Schrödinger was the first to solve. Ĥ  E
Only case where we can solve the Schrödinger equation exactly.
As soon as we consider He atom with ( 2e  + nucleus), we have to resort to approximations /

computations.
The Hamiltonian for – H-atom can be written as:

Potential

H  K.E of l  K .E of nucleus + Coulomb attraction.
1 2 1 2 e2
pe pN
2 me 2 mN 4 0 r
r 2   xN  xe    yN  ye    Z N  Z e 
2 2 2
In QM approach:
ˆ 1 2 1 e2
H pe 
ˆ pN 
ˆ 2
2me 2 mN 4 0 r
    
pˆ e  i  iˆ  ˆj  kˆ 
 xe ye ze 
Similarly,
    
pˆ N  i  iˆ  ˆj  kˆ 
 xN y N zN 
    
 pˆ e2   2
 2  2  2    e
2 2
 xe ye ze  
“Laplacian”
As usual, we are interested in the internal is electronic motion and not the translation part of the atom.
 let’s go to center of mass and relative co-ordinates


r  rN  re
Then motion (internal) described by reduced mass  ,

mm
  e N  me
me  mN
Then,
 2 2 e2
Hˆ relative   
2 4  0 r
We will be discussing the solution to the Schrödinger equation for the hydrogen atom.
We will solve Ĥ  E to get quantized energies as:
13.6
En  eV
n2

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Lecture 9

Recap of Toy problems & Introducing H-atom

Angular Momentum :  can be indefinite, Energy can be definite (zero).

Clearly, quantum state now   ,  

One quantum number is associated with  : ml => precession about z-axis.

(This is written in spherical polar coordinates )

This is a partial differential equation. The solutions are known,

Ylml  ,    N lml Pl ml  cos   eiml

Now, l is the other quantum number apart from ml .

 They are eigenfuctions of Hˆ , Lˆ and Lˆ .

  E  0,  LZ  0 and Square of Ang. Mom. is known with certainty.

* But Ylml are not eignfunctions of Lˆ x and Lˆ y .

Now, note that Energy does not depend on ml !

In fact, since ml  0, 1, 2,...., l there is a degeneracy of  2l  1 .

Reason that Energy is independent of ml is because our choice of Z -axis is arbitrary. We

Clearly,   Y10  ,   , Y1,1  ,   , Y1,1  ,  

LˆZ Y1,1  ,       Y1,1  ,  

L 2 ; Since L > max. value of LZ

 L and LZ cannot in same direction!

L2x  L2y  L2Z  L2  2 2

* Projected Motion in x-y plane

Now, for any 2-particle system undergoing rotational motion,

Bohr, introduced the concept of quantization, Energy in terms of a integer.

(Rutherford, before that, argued the ‘planetary model’)

Problems with classical

Bohr : Certain orbits stable.

Why QM provides the answer.

Schrödinger was the first to solve. Ĥ  E

Only case where we can solve the Schrödinger equation exactly.

As soon as we consider He atom with ( 2e  + nucleus), we have to resort to approximations /

The Hamiltonian for – H-atom can be written as:

 xe ye ze  

 let’s go to center of mass and relative co-ordinates

Then motion (internal) described by reduced mass  ,

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