Lecture-II

Quantum mechanics is the only

way to truly understand:

• The nature of atoms

• The structure and properties
of molecules
Wave-particle Duality

• An important quantum mechanical

concept

• The inherent property of any

system to behave like a wave
or behave like a particle,
depending on the nature of the
experiment
X-Ray Diffraction

• Waves can exhibit the physical

phenomena known as diffraction.
• Used for determining the structure
of molecules.
• Diffraction takes advantage of the
wave nature of light, just as one can
use a diffraction grating to separate
lights into different colors.
Electron Diffraction

• Davisson and Germer (1927)

showed that not only could one
diffract light, but one could
diffract electron as well.
 The Schrödinger Equation

ĤΨ=EΨ
Solving for the Schrodinger Equation

The Schrodinger Equation tells us

how to find the wave functions and
energies for a quantum system
Finding Discrete Solutions

Imposing boundary conditions

on the Schrödinger Equations
leads to the discrete energy
solutions that are the hallmark
of quantum mechanics
 Energy Levels

The energy spectrum of matter

can only be discrete
The classical mechanics
of the harmonic oscillator
Diatoms and Vibrational Frequency

The relative motion between the

two atoms in a diatomic molecule
can be described as a
harmonic oscillator.
 Harmonic Oscilator Solutions to
Schrodinger's Equation

The wave functions and energies

for a quantum mechanical harmonic
oscillator are obtained from the
solutions of Schrodingers equation.
 The Rigid Rotor

Molecular Rotation
The angular motion of a diatomic
molecule can be described as a
rigid rotor
Spherical Polar Coordinates

The quantum mechanics of

a rigid rotor are best solved
for in a spherical polar
coordinate system
The eigenfunctions and energies of
the quantum mechanical rigid rotor
are obtained from the solutions of
Schrödingers equation
 The Hydrogen Atom

The six basic assumptions of

quantum mechanics can be
applied to the hydrogen atom.
The Hamiltonian and Wave Functions
for the Hydrogen Atom

The angular motions of the electron

in the hydrogen atom are described by
functions known as spherical harmonics
Radial part

Angular part,
Spherical harmonics
 Quantum Numbers

The states of the hydrogen atom

are characterized by three
quantum numbers, while the
energies only depend on one
quantum number.
 Real Solutions from
Complex Functions

Complex eigenfunctions of the

hydrogen atom can be made completely
real by taking the appropriate linear
combinations of the
degenerate eigenfunctions
 Wave Functions and Orbitals

Wave functions
mathematically describe an electron
are composed of radial and angular
components

can be numerically positive or negative

depending on position
Orbitals
describe the probability of an electron
being at a certain position
are positive values calculated by squaring
the wave function
 Atomic orbitals: 1s equations

Function Equation
Radial wave function, R1s = 2 × Z3/2 × e-ρ/2
Angular wave function, Y1s = 1 × (1/4π)1/2
Wave function, ψ1s = R1s × Y1s
= 2Z3/2e-ρ/2 ×
(1/4π)1/2
Electron density = ψ1s2
Radial distribution function = 4πr2ψ1s2

ρ = 2Zr/n
Atomic orbitals: 1s wave function
 Radial Function
3/2
Z −Zr/ao
R = 2   e 1s
 ao 

52.9 pm
R R2 r2R2

r r r
radial electron electron
wave function density probability
 Table of equations for the 2s orbital.

Function Equation
Radial wave function, R2s = (1/2√2) × (2 - ρ) × Z3/2 × e-ρ/2
Angular wave function, Y2s = 1 × (1/4π)1/2
Wave function, ψ2s = R2s × Y2s
Electron density = ψ2s2
Radial distribution function = 4πr2ψ2s2
Atomic orbitals: 2s wave function
 Radial Function
3/2
 1  Z   Zr  −Zr/ao 2s
R=     2 -  e
 2 2   ao   ao 

~220 pm
R R2 r2R2

r r r
radial electron electron
wave function density probability
Table of equations for the 2p orbital

Function Equation
Radial wave function, R2p = (1/2√6) × ρ × Z3/2 × e-ρ/2
Angular wave function, Y2px = √(3)x/r × (1/4π)1/2
Wave function, ψ2px = R2p × Y2px
Electron density = ψ2px2
Radial distribution function = r2R2p2
 Radial Function
3/2
 1  Z   Zr  −Zr/2ao
R=      e 2p
 2 6   ao   ao 

~210 pm
R R2 r2R2

r r r
radial electron electron
wave function density probability
 Table of equations for the 3d orbitals.

Function Equation
Radial wave function, R3d = (1/9√30) × ρ2 × Z3/2 × e-ρ/2
Angular wave functions:
Y3dxy = √(60/4)xy/r2 × (1/4π)1/2
Y3dxz = √(60/4)xz/r2 × (1/4π)1/2
Y3dyz = √(60/4)yz/r2 × (1/4π)1/2
Y3dx2-y2 = √(15/4)(x2 - y2)/r2 × (1/4π)1/2
Y3dz2 = √(5/4){2z2-(x2 + y2)}/r2 × (1/4π)1/2
Atomic orbitals: 3d
 Angular Function
The lobes of an orbital result from the angular
portion of the wave function.

1 1
ΦΘ = ⋅ s
2π 2
1 6
ΦΘ = ⋅ cos θ p0
2π 2
1 iφ 3
ΦΘ = e ⋅ sin θ p+1
2π 2
1 − iφ 3
ΦΘ = e ⋅ sin θ p-1
2π 2
 Angular Function
The lobes of an orbital result from the angular
portion of the wave function.
1
ΦΘ = s
2 π

ΦΘ =
3
cos θ pz
2 π
3
ΦΘ = sin θ cos φ px
2π
3
ΦΘ =
2π
sin θ sin φ py
 Wave Functions and Orbitals
The lobes of orbitals are sometimes identified
with the numerical sign of the wave function.

- +
- + + -
-
+
+ - -
- +

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