GENERAL CHEMISTRY (CHEM F111)

Lecture 7: 04/11/2022

Recap
 Particle in a two dimensional box
 Symmetry of the box and Degeneracy
 One dimensional Harmonic Oscillator
Particle on a sphere (Rigid rotator)
Three dimensional Systems Spherical Polar coordinates

It is convenient to describe the solutions of the

Schrödinger equation in spherical polar
coordinates (r, ,) rather than cartesian (x,y,z)
Spherical coordinates
 Rigid rotator
Rotation in Three Dimensions

 2  1   2   1     1  2 
 2 r  2  Sin  2 2 2
 E
2m  r r  r  r Sin     r Sin   

Not needed for you

 •Particle constrained to rotate on surface of
sphere of radius r

• Classically, E = L2/2mr2 = L2/2I

Schrodinger equation involves the polar angle (colatitude) θ
and the azimuthal angle φ as variables
Rigid Rotor

Wave functions must contain both θ and Φ

dependence:

are called spherical harmonics

•On solving the Schrodinger equation, and imposing the

appropriate boundary conditions, obtain the ‘spherical harmonics’
Yl,ml(,), characterized by two quantum numbers l and ml as
solutions
Particle on a sphere
El = l(l + 1)ħ2/2I
Quantum number l allowed to take on values
0,1,2,…

For a given value of l, the quantum number m can

take any of the 2l + 1 values -l, -(l +1),…, 0,…, l-1, l
Degeneracy of energy level = 2l + 1
Energy does not depend on the quantum number
ml
Rigid Rotor – Angular Momentum

• Quantum number l may take on values 0,1,2,…

• Magnitude of the orbital angular momentum

J = [l(l + 1)]1/2ħ

• For a given value of l, the quantum number ml can

take any of the 2l + 1 values -l, -(l +1),…, 0,…, l-1, l.

• mlħ is the value of, say, the z-component of the

orbital angular momentum
 Angular Momentum

Quantum number l may take on values 0,1,2,…

Magnitude of the orbital angular momentum
J = [l(l + 1)]1/2ħ
For a given value of l, the quantum number ml can
take any of the 2l + 1 values -l, -(l +1),…, 0,…, l-1, l.
mlħ is the value of, say, the z-component of the
orbital angular momentum
Quantization of the Angular Momentum

• Two aspects of the quantization of the angular momentum

vector, the magnitude and the direction
• The magnitude is [l(l + 1)]1/2ħ
• Any spatial component, say z-component of the angular
momentum, may only take one of the values mlħ, where
•for a given l, ml may take on one of the 2l+1 values -l, -
(l+1),...0,..., l-1, l. If one component specified precisely, the other
two cannot.
• In other words, the angular momentum vector may only make
one out of a discrete set of 2l+1 angles with any chosen axis in
space, say the z-axis
l=1;
(Total angular momentum L =[l(l+1)]ħ = 2 ħ
ml = 1, 0 or –1
Solution of Schrödinger Equation for some
Real Chemical Systems
Hydrogenic systems

One electron atom or ion of general atomic

number Z : H (Z=+1 and 1 electron);
He+ (Z=+2 and one electron), Li2+ ,Be3+ ,
C5+ etc.
EXACT solution is possible !
Many electron systems : not possible to solve
Schrödinger eqn. exactly
Hydrogen has special significance
•No approximation is required in solving the
Schrödinger equation
•Can get exact expression for energy levels
•Spectral frequencies can be deduced
 Hydrogenic System
It has three dimensional features Ψ (x,y,z)

Form of Schrödinger equation:

Ĥ Ψ (x,y,z) = E Ψ (x,y,z)
 Hydrogenic Systems
Schrödinger equation: Ĥ Ψ (x,y,z) = E Ψ (x,y,z)

2 2 2
    2
2 -Laplacian Operator
x 2 y 2 z 2

 2 2 
   V ( x, y, z ) ( x, y, z )  E ( x, y, z )
 2m 