BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Semester II: AY 2021-22
Lecture- 05, 20 May 2022, Friday

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Announcement

Extra class for Lecture section: L-1

Instructor: Dr. S. C. Sivasubramanian

Date: Tuesday, 24 May 2022

Time: 6:00 p.m.
Venue: Class Room # 5102

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General Chemistry
Last Class:
Vibrational motion
• Classical and quantum pictures; Hamiltonian operator (both kinetic
and potential energies); wave function (3 parts – normalization
constant, Hermite polynomial, exponential factor); energies En = (n
+ ½) hν ; zero-point energy hν/2; even spacing; Large n values –
classical picture – correspondence principle.
Motion on a circular path
• No potential energy; angular momentum; Hamiltonian operator
polar coordinates only one variable; cyclic boundary conditions 
𝟏
mλ = 2πr; normalized wavefunction 𝒆𝒊𝒎𝝓 ; energy = m2ℏ2/2I;
𝟐𝝅
m = 0,   ….; degeneracy; no zero point energy; angular
momentum = mlℏ (quantized).
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Particle on a Sphere

Example 4: Application of Quantum Mechanics to

Particle on a Sphere (3-D Rigid Rotor)
z

r y

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Rotation in three dimensions
• Consider a particle moving on the surface of a sphere.
• Understanding this rotational motion in three dimensions will help
us understand the motion of electrons around nuclei in atoms.
• Study of molecular rotations gives us bond lengths etc.
V=0
• Two angles (particle confined to a spherical space)
 - the azimuthal angle
z
θ - the colatitude Pilani 28.3802° N, 75.6092° E ???

 x, y, z     ,  
• Motion of a particle over sphere is like r y
motion of particle over a stack of rings, with
additional freedom to migrate between
rings.
  ,         x

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Spherical polar  Cartesian

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Hamiltonian operator in polar coordinates

ˆ  2
H  2  Vˆ
2m

  2
 2
 2


  2 
2
 2  …….. Cartesian coordinates
x y z 
2

  2
2  1  1  2
1     
  2 
2
 2 2  
 sin   
 

r     2
       
 r r r  sin sin
…… polar coordinates
Since r is fixed
1  1 2 1     
  2
2
 2   sin  
r    
 sin    sin    
2

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The Schrödinger equation: Particle on a
sphere
1  1 2 1     
  2
2
 2   sin   r constant
r    
 sin    sin    
2
 V=0
I = mr2
Laplacian Legendrian
Operator Operator  2

 1 2   2
  2  
2
Hˆ   2  Vˆ
r  2m
The Schrödinger equation: Ĥ=E
 2  1 2 
 2       E     E  ,  
2m  r 
NEXT: Solving the Schrodinger equation and applying the appropriate
cyclic boundary conditions
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Particle on a sphere rigid rotor:
Boundary Conditions
• Two variables : Polar angle – colatitude  & Azimuthal angle ϕ;
• The problem can be visualized as a set of “particle in a ring” problems
with the addition of movement between rings.
• Imposing first boundary condition: The acceptable wavefunction
must describe the motion of the particle round the equator or any
parallel ring.
That means ϕ = 0 to 2π and this brings in the quantum number, ml
(similar to particle in a ring).
• Imposing second boundary condition: The acceptable wavefunction
must describe the motion of the particle across the poles.
That means  = 0 to π; and this constraint introduces a second
quantum number l called orbital momentum quantum number.

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Particle on a Sphere - Rigid Rotor:
Acceptable solution of wavefunction
• Rigid = fixed r; molecular rotations – fixed bond length;
• The acceptable solutions for the wavefunctions happens
to be:
•  l ,ml  ,   = Yl,ml( , ϕ) = Θl,ml( )Φml(ϕ)
Spherical harmonics
iml
Yl,ml( , ϕ)  Polynomiall , m ( ).
e
l
2 1/ 2

such that l = 0,1,2...

For a given value of l there are 2l+1 permitted values of
the magnetic quantum no. ml. (ml = l, l-1,……,- l )
Each set of quantum numbers (l, ml) represent a unique state.
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Particle on a Sphere – Rigid Rotor:
Acceptable Solutions of Wavefunction
•Yl,ml could be imagined as wave like distortions on a
spherical shell.
l ml Yl,ml( , ϕ)
0 0
1 0
±1
2 0
±1
±2
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Particle on a Sphere – Rigid Rotor:
Acceptable Solutions of Wavefunction
Yl,ml( , ϕ)

Connected to
Associate
Legendre
Polynomials

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Particle on a sphere rigid rotor:
Energy & Momentum
• The solution of Schrodinger eq. also gives the energy, E of the
particle restricted to the values:
Energy = l(l + 1)ħ2/2I l = 0,1,2,3…. I=mr2
Energy is quantized and is independent of ml
• A level with quantum no. l is (2l+1) fold degenerate.
Degeneracy = (2l+1)
• L = [l(l + 1)]1/2ħ Total Angular momentum is Quantized
• z-component of the angular momentum,
Lz = mlħ (HUP: Lx and Ly are now not precisely known)
for a given l, ml may take on one of the 2l+1 values (-l,
-(l+1), ...0, ..., (l-1), l)
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Space Quantization- Lz
Two aspects of the quantization of
angular momentum vector (L), are
the magnitude and its orientation.
For each l, there could be limited ml
values,
the orientation of a rotating body is
quantized.

For a particle having a certain energy

(e.g. characterized by l=2), the plane of
rotation can only take a discrete range
of orientations (characterized by one
of the 2l+1 values ml)
Space quantization
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Vector Model of Angular Momentum Lz

Case l = 2, ml = 2, 1, 0, -1, -2

Lz
L

L is a vector (Lx and Ly are not precisely known).

L lies on the surface of a cone.
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Atoms

Hydrogen Atom
& Hydrogen like Species (Hydrogenic)
(one electron systems)

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Hydrogen Atom
• Atom = 1 electron (me) and 1 nucleus of mass mN.

• The atom is a 2-body system: both the nucleus and e- move with
respect to each other (relative motion) and both move with respect
to an outside reference point (motion of the centre of mass).

• Because of the electronic charge and the positive charge |Ze| of

the nucleus, the potential energy V(r) has to be taken into account
in the energetics of the system.
2 Note: The potential is spherically
Ze
V(r) = - symmetric, i.e., it depends only on
4 0 r the distance r.

• Since mN >> me, the nucleus may be taken to be at rest, and the
electron moving about it.
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Hydrogenic Atoms: The Hamiltonian
The Hamiltonian for internal motion of the electron relative to the
nucleus is

ˆ (   2
)   2
 2
 2
 ˆ
H  2     V (r )
2 
2   x  y 2
y 
mn me …….. Cartesian coordinates

mn  me
2  
  2
2  1  1  2
1     
Hˆ      2 2   sin     V (r )
2   r 2
r  r r  sin    2
sin        
……….. Hamiltonian operator in polar coordinates

  2  1 2 
 
2 2
ˆ 
H   2   2    V (r )
2   r r r r 
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Hydrogenic Atoms: Schrödinger Equation

Hˆ  (r , ,  )  E (r , ,  )
 (r , ,  )  R(r )     R(r ) Y ( ,  )
 2  2 2  1 2  
  2   
 2    V (r )[ R(r )   ]  E[ R(r )   ]
 2   r r r r  

• Solving the Schrodinger equation and applying the

appropriate boundary conditions:
r = 0 to ∞ ϕ = 0 to 2π  = 0 to π

 n,l ,m (r , ,  )  Rn,l (r )l ,m    m    Rn,l (r ) Yl ,m ( ,  )

l l l l

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Hydrogenic Atoms: Schrödinger Equation

 n,l ,m (r , ,  )  Rn,l (r )l ,m    m    Rn,l (r ) Yl ,m ( ,  )

l l l l

•In this case the Schrӧdinger equation is solvable

due to spherically symmetric potential;
• These solutions are called “Atomic Orbitals”;
• Thus “Atomic Orbitals” are one electron
wavefunctions;
• This solution corresponds to spatial part only; spin
will be added later.
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Hydrogenic Atom: Meaning

• Hydrogenic Atoms Hydrogen Like one

electron systems

Examples: H, He+, Li+2 , C5+, U91+

For these systems also

SchrÖdinger Equation can be solved.

Exact Analytical Solutions of are possible.

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Hydrogenic Atoms : Boundary conditions

Hˆ  (r , , )  E (r , , )
 n,l ,m (r , ,  )  Rn,l (r )l ,m    m    Rn,l (r ) Yl ,m ( ,  )
l l l l

Such that: Radial part of

n = 1,2,3….. wavefunction
l<n Angular part of
│ml │≤ l (-l to l) wavefunction
• The angular part of the solution is the same for a particle in any
spherically symmetric potential.
iml
e
Yl,ml( , ϕ)  N l ,ml polynomiall ,ml ( ).
2 1/ 2

Normalization constant Associated Legendre polynomial

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Hydrogenic Atoms: Angular Solution
• The magnitude of angular • z-component of angular
momentum (L): = [l(l + 1)]1/2ħ momentum (Lz) = mlħ
l can take on the values 0,1,2,3,...,n-1 with ml = l, l-1,…,-l
(2l+1) values of ml

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