CHEMF111 Lecture5 Aug12 2016 - BPHC

General Chemistry
CHEM F111
Lecture 5
12.08.16
Recap of Lecture 4
Particle in a One Dimensional Box
Characteristics of the Wavefunctions

Particle in a Two Dimensional Box Separation of
Variables
Square Box Degeneracy
Tunneling
Recap of Lecture 4
Boundary condition in one dimension :
1 Quantum number
in two dimensions :
2 Quantum numbers
in three dimensions :
3 Quantum numbers
Preview of Lecture 4
Vibration - Harmonic Oscillator model
Rotation in Three Dimensions Rigid Rotator

Quantization of Orbital Angular Momentum
Hydrogenic Atom- Energy Levels and Wavefunctions
Vibration: Harmonic Oscillator
Hookes law: Restoring force = kx

displacement from equilibrium)
Potential energy V(x) = kx2
( k force constant, x
Harmonic Oscillator - Energy Levels

Solve the Schrodinger equation and apply the
boundary conditions ( as x ) to get:
Ev = (v + )h,
v = 0,1,2,. is the vibrational quantum number, and
= (1/2)(k/m)1/2 is the vibrational frequency
Evenly spaced energy levels.

Spacing = h
Ground state energy = h
(Zero point energy)
Harmonic Oscillator - Wavefunctions
Characteristic Features
1. Number of nodes is v.
2. Wavefunctions
alternately
antisymmetric about x = 0.
symmetric
or
3. One can show that as v becomes large, the probability

distribution resembles the classical result.
4. The wavefunction leaks into the classically forbidden
region TUNNELING
Harmonic Oscillator Wavefunctions - Tunneling
Rotational Motion
Angular Momenta
Shapes of electron probability distribution in atoms
Rotations of molecules structural information
Central importance in chemistry
Rotation in Three Dimensions Rigid Rotor

Particle constrained to rotate on surface of sphere of
radius R
Classically, E = J2/2mR2 = J2/2I
Schrodinger equation
involves the polar angle
(colatitude) and the
azimuthal angle as
variables
Solutions apply to all problems where

the potential is spherically symmetric
Rigid Rotor Wavefunctions

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
The spherical harmonics are a product of two
functions, Yl,ml(,) = lml()ml()
El = l(l + 1)2/2I
Quantum number l allowed to take on values 0,1,2,
Rigid Rotor Energy Levels

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
In absence of any perturbing field, or in presence of
spherically homogeneous field, the 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)]1/2
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.
ml is the value of, say, the z-component of the orbital
angular momentum, along the direction of the external
field, if any.
Case l = 1, ml = 1, 0, -1
Case l = 2, ml = 2, 1, 0, -1, -2
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)]1/2
Any spatial component, say z-component of the
angular momentum, may only take one of the values
ml, 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
Hydrogen-like (Hydrogenic) Atom

Atom with a nucleus of charge Ze and mass mN, and a
single electron of charge e and mass m. The two interact
according to the Coulomb potential
V(r) = Ze2/r
where r is the distance between the two particles, and is
the vacuum permittivity.
Note that the potential is spherically symmetric, ie., it
depends only on the distance r
Other example: He+ (Z=+2 and one electron), Li2+ , Be3+ ,
C5+ etc.
Exact Solution of Schrodinger equation is possible !
Schrdinger equation: = E
2
2
2 2
[ 2 2 2 ] V ( x, y, z ) ( x, y, z ) E ( x, y, z )
y
z
2m x
2
2
2
2
x 2 y 2 z 2
2 -Laplacian Operator
2 2
V ( x, y, z ) ( x, y, z ) E ( x, y, z )
2m
Spherical Polar Coordinates

Given the spherical symmetry of the potential V, the Schrodinger
equation is most conveniently treated in spherical polar
coordinates by the separation of variables method.
2 2
Ze2
( x, y, z ) E ( x, y, z )

4 0 r
2m
Particle in a sphere
Hydrogenic Atom Wavefunctions

The wavefunctions for the hydrogenic atom, in spherical
polar coordinates, may be shown to factor as
(r,,) = R(r)()()
Further, the requirement that the wavefunction be wellbehaved, leads to the result that the functions are labeled
by three quantum numbers n, l, and ml ie.,
n,l,ml(r,,) = Rn,l(r)l,ml()ml() = Rn,l(r)Yl,ml(,)

Wave functions of the electron are called atomic orbitals;
where Rn,l(r) is called the radial part and Yl,ml(,) its
angular part.
The angular parts are the same for a particle in any
spherically symmetric potential
Boundary Conditions for Hydrogen atom

1. must vanish as the electrons goes to infinity
2. must match as the electrons encircles the poles
3. must match as the electron moves

around the equator
Each condition gives rise to a quantum number that specifies
The address of the electron in the atom (n, l and ml)
Solution of Radial Equation: Energy Levels of the

Hydrogenic Atom
The
energy
levels
are
given
by
En = e4Z2/32n2 = -hcRZ2/n2 with n =
1,2,3,.
The energy depends only on the principal
quantum number n, (and not on l or ml). Note
the dependence -------> Energy levels
Here the reduced mass = mmN/(m+mN) m
Note the dependence of the energy on Z2, and
the negative sign. Ionization energy of H?

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General Chemistry

Characteristics of the Wavefunctions

Rotation in Three Dimensions Rigid Rotator

Hydrogenic Atom- Energy Levels and Wavefunctions

Vibration: Harmonic Oscillator

Hookes law: Restoring force = kx

Harmonic Oscillator - Energy Levels

Evenly spaced energy levels.

Harmonic Oscillator - Wavefunctions

3. One can show that as v becomes large, the probability

Harmonic Oscillator Wavefunctions - Tunneling

Central importance in chemistry

Rotation in Three Dimensions Rigid Rotor

Solutions apply to all problems where

Rigid Rotor Wavefunctions

Rigid Rotor Energy Levels

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

Rigid Rotor Angular Momentum

Quantization of the Angular Momentum

Hydrogen-like (Hydrogenic) Atom

Spherical Polar Coordinates

Hydrogenic Atom Wavefunctions

n,l,ml(r,,) = Rn,l(r)l,ml()ml() = Rn,l(r)Yl,ml(,)

Boundary Conditions for Hydrogen atom

3. must match as the electron moves

Solution of Radial Equation: Energy Levels of the

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