Module-2

Quantum Chemistry
 Evolution of Quantum mechanics

1922: 1925: 1940:

Heisenberg Pauli proves
Neils Bohr
Uncertainty Spin-Statistic
won Nobel
principle Theorem
Prize in
physics Wolfgang Pauli
spin number 1932: 1944:
1918: Werner
Heisenberg
1905: Max Planck won
Nobel prize in
won Nobel 1936: Pauli won
Nobel Prize in
Albert proposed the Prize in Schrödinger's physics
physics physics
idea photoelectric Equation
effect.

1924: 1929: 1933: 1943:

1921: Louis De Broglie
1900: 1913: Won the Nobel
electron waves. Louis De Otto Stern
Broglie won measures the
Otto Stern Nobel
Prize in Physics prize in Physics
Max Planck Neils Bohr the Nobel magnetic
black-body photoelectric Prize. moment of the
atomic structure
radiation effect. proton
 Structure of the Atom
• In 1909, the prevailing theory of
atomic structure was the plum
pudding model.

• In this model, proposed by J. J.

Thomson, the electrons were thought
to be floating around in a soup of
positive charge. [Link]
%3A_Chemistry_for_Changing_Times_(Hill_and_McCreary)/03%3A_Atomic_Structure/
3.04%3A_Rutherford's_Experiment-_The_Nuclear_Model_of_the_Atom
 Rutherford’s Atomic Model
Ernest Rutherford (Cambridge University, England, 1871-1937) studied α emission from newly-
discovered radioactive elements.
"It was almost as incredible as if you fired a fifteen-inch shell
at a piece of tissue paper and it came back and hit you"
 Rutherford’s Atomic Model
Drawback
• According to classical theory, atoms in the model for Rutherford’s are not stable.
• The motion of moving electrons should cause them to radiate energy in their orbits and to quickly
execute a death spiral and collapse into the nucleus.
• The time taken for this collapse is estimated around 10 −8 s, which is very small. According to the
model, every atom will crumple in 10 −8 s, but we know this is not reality.
• If the electrons are not revolving but stationary, still the electrons will fall into the nucleus by the
electrostatic force between both. The predicted death spiral of the electron!
Hydrogen Atomic Spectrum
 Hydrogen Atomic Spectrum

• When a high-energy discharge is passed through a sample of H2 gas, the H2 molecules absorb energy,
causing some of the H-H bonds to break.
• The resulting hydrogen atoms are excited; they contain excess energy, which they release by emitting
light of various wavelengths to produce what is called the emission spectrum of the hydrogen atom.,
called a line spectrum.
• Do the electrons in atoms and molecules obey Newton’s classical laws of motion?

• It turns out that the laws of classical mechanics no longer work at this size scale.

• A new kind of mechanics was needed to describe this and other “unsettling” observations.
 Classical Mechanics
• Classically, particles and waves are distinct:
– Particles – characterised by position, mass, velocity.
– Waves – characterised by wavelength, frequency.

𝜆𝜈=𝑐
 Classical Mechanics

By the 1920s, however, it was becoming apparent that sometimes matter (classically
particles) can behave like waves and radiation (classically waves) can behave like particles.
 The Photoelectric Effect

A beam of light hitting a metal surface can cause

electrons to be ejected from the surface.

Classical Paradigm: the energy of the ejected

electrons should be proportional to the intensity (I) of
the light and independent of the frequency (𝝂) of the
light.

Experiment: the energy of the ejected electrons is

independent of the intensity (I) and depends directly
on the frequency (𝝂) of the light.
 The Photoelectric Effect
The following observations characterize the photoelectric effect.
1. No electrons are emitted by a given metal below a specific threshold frequency 𝝂0.

2. For light with frequency lower than the 𝝂0, no electrons are emitted regardless of the intensity of the light. For light

with frequency greater than the 𝝂0, the kinetic energy of the emitted electrons increases linearly with the frequency of
the light.
3. The number of electrons emitted per second (i.e. the electric current) is independent of light frequency above the 𝝂0
and zero below.
[Link] light with frequency greater than the 𝝂0, the number of electrons emitted increases with the intensity of the
light.
 Quantization of Light

The slope of KE vs  is h

Workfunction, ɸ
 Quantization of Light

• These observations can be explained by assuming that

electromagnetic radiation is quantized (consists of photons) and
that the threshold frequency represents the minimum energy
required to remove the electron from the metal’s surface.
• Minimum energy required to remove an electron, E0 = h0

nhc
E (n 0,1, 2,3,.......)

 Quantization of Light

NOT

Waves behaving as Particles

 Example

• What is the energy in joules and electron volts of a photon of 420-nm violet light?
• What is the maximum kinetic energy of electrons ejected from calcium by 420-nm violet light, given that the
workfunction for calcium metal is 2.71 eV?
 Example

• What is the longest-wavelength electromagnetic radiation that can eject a photoelectron from silver? Is this in
the visible range? Given that the workfunction of silver is 4.72 eV.

• Only photons with wavelengths lower than 263 nm will induce photoelectrons.

• This is ultraviolet and not in the visible range.

 Wave Nature of Particles

• Louis de Broglie postulated that as light has wave-like and particle-like

properties, matter must also be both particle-like and wave-like.

• A particle, of mass m, travelling at velocity v, has linear momentum p = mv.

• By analogy with photons, the associated wavelength of the particle () is given
by:

h h
de Broglie wavelength λ  de Broglie’s equation
p mv

The fact that particles can behave as waves but also as particles, depending on
which experiment you perform on them, is known as the particle-wave duality.
 • Bullets are far more massive than the electrons.
One can observe them as long as one likes but it
would not make any difference to them.
• The interference wiggles in the case of bullets are
so crowded that it is physically impossible to
resolve them, one sees an average behaviour

The wave properties of matter are only apparent

for very small masses of matter.
 Wave Nature of Particles:
Validation
According to classical physics, electrons should behave like
particles - they travel in straight lines and do not curve in
flight unless acted on by an external agent.
In this model, if we fire a beam of electrons through a
double slit onto a detector, we should get two bands of
"hits”.

Can be explained only in terms of waves.

 Wave Nature of Particles:
Validation
• Davisson and Germer showed that a beam of electrons could be diffracted from the surface of a nickel crystal.
• Scattered light can interfere constructively (the peaks and troughs of the beams are in phase) to produce a
bright area or destructively (the peaks and troughs are out of phase) to produce a dark spot.
• A diffraction pattern can be explained only in terms of waves.

NB: Other “particles” (e.g. neutrons, protons, He atoms) can also be diffracted by crystals.
 Wave-Particle Duality

• Now we have come full circle.

• Electromagnetic radiation, which at the turn of the twentieth century was thought to be a pure

waveform, was found to exhibit particulate properties.

• Conversely, electrons, which were thought to be particles, were found to have a wavelength

associated with them.

• Energy is really a form of matter, and all matter shows the same types of properties.

• All matter exhibits both particulate and wave properties.

 Putting it All together: The Bohr Atom

E4
E3
• Bohr proposed a model that included the idea that the
E5 E2
electron in a hydrogen atom moves around the nucleus only
E1
in certain allowed circular orbits.
• Bohr assumed that the hydrogen electron could exist only in
stationary, non-radiating orbits.
 Putting it All together: The Bohr Atom

Solving Paradox I: The unstable orbiting electron of Rutherford’s atom.

• Make the orbiting electron stable by assuming that the electron’s orbit and
energy is quantized to certain values and for these values the orbiting
electron does not radiate.
• The electron is stable in these orbits.
• Thus, the orbits and energies of electrons are quantized.

Solving Paradox II: The line spectra of emitting or absorbing atoms.

• Since only certain energies are allowed for orbiting electrons, only jumps
between orbits can be observed.
• These jumps correspond to discrete frequencies and wavelengths.
• Thus, line spectra as expected because of the quantized energies of the
orbits.
• In the Bohr atom, the circular symmetry and the wave property of the electron requires that the
electron waves have an integer number of wavelengths.
• If not, then the waves will overlap imperfectly and cancel out (i.e., the electron will cease to exist).

[Link]
 The Bohr Atom

• Light is emitted when an electron jumps from a higher orbit to a lower orbit and absorbed when it jumps from a
lower to higher orbit.
• The energy and frequency of light emitted or absorbed is given by the difference between the two orbit energies,
e.g.,
• E(photon) = E2 - E1 (Energy difference) = h𝝂 𝒉𝒄
𝜟 𝑬 =𝒉𝝂 =
𝝀
 The Bohr Atom

E4 E2 - E1 = hn
E
E5 3
E2
E1
5
4
3 Photon
Absorbed
2

1
410.1 434.0 486.1 656.3
nm nm nm nm

Bohr atom: Light absorption occurs when an electron absorbs a photon and makes a transition for
a lower energy orbital to a higher energy orbital. Absorption spectra appear as sharp lines.
 The Bohr Atom

E2 - E1 = hn
E4
E3
E5 E2
5 E1
4
3
Photon
2 Emitted

1
410.1 434.0 486.1 656.3
nm nm nm nm

Bohr atom: Light emission occurs when an electron makes a transition from a higher energy
orbital to a lower energy orbital and a photon is emitted. Emission spectra appear as sharp
lines.
 The Bohr Atom

Limitations of Bohr Model

• At first, Bohr’s model appeared to be very promising.

• The energy levels calculated by Bohr closely agreed with the values obtained from the hydrogen

emission spectrum.

• However, when Bohr’s model was applied to atoms other than hydrogen, it did not work at all

• The model only works for hydrogen (and other one electron ions) – ignores e-e repulsion.

• Does not explain fine structure of spectral lines.

• Note: The Bohr model (assuming circular electron orbits) is fundamentally incorrect.
 Heisenberg’s Uncertainty Principle

• Bohr orbit: The electron in the orbital is moving around the nucleus in a circular orbit.

• We can predict the motion of the electron, similar to the motions of particles in the macroscopic

world.

• For example, when two billiard balls with known velocities collide, we can predict their motions

after the collision.

• Werner Heisenberg, discovered a very important principle in 1927—the Heisenberg uncertainty

principle.
 Heisenberg’s Uncertainty Principle

• The Heisenberg Uncertainty Principle is a fundamental theory in quantum mechanics that defines why a
scientist cannot measure multiple quantum variables simultaneously.

• Heisenberg made the bold proposition that there is a lower limit to this precision making our knowledge
of a particle inherently uncertain.

• There is a fundamental limitation to just how precisely we can know both the position and the momentum
of a particle at a given time.

ℏ = ℎ/2𝜋

where Δx is the uncertainty in a particle’s position, Δp is the uncertainty in a particle’s momentum.

Note: There is no restriction on the precision in simultaneously knowing/measuring the position along a
given direction (x) and the momentum along another, perpendicular direction (z):
Δpz. Δx = 0
 Making Sense of the Uncertainty Principle

• To localize a particle in space (i.e. to specify the particle’s position accurately, small Δx) many
waves of different wavelengths () must be superimposed  large Δpx (p = ℎ/).

• The Uncertainty Principle imposes a fundamental (not experimental) limitation on

how precisely we can know (or determine) various observables.

[Link]
An electron is confined to the size of a magnesium atom with a 150 pm radius. What is the minimum
uncertainty in its velocity?
Determine the uncertainty in the position of the ball (163 gm) bowled
at with velocity of 111 kph.
The hydrogen atom has a radius on the order of 0.05 nm. Assuming that we know the position of an electron to an
accuracy of 1% of the hydrogen radius, calculate the uncertainty in the velocity of the electron using the Heisenberg
uncertainty principle. Then compare this value with the uncertainty in the velocity of a ball of mass 0.2 kg and
radius 0.05 m whose position is known to an accuracy of 1% of its radius.

Thus the uncertainty principle is

negligible in the world of
macroscopic objects but is very
important for objects with small
masses, such as the electron.
• This limitation is so small for large particles such as baseballs or billiard balls that it is

unnoticed.

• However, for a small particle such as the electron, the limitation becomes quite

important.

• Applied to the electron, the uncertainty principle implies that we cannot know the exact

path of the electron as it moves around the nucleus.

• It is therefore not appropriate to assume that the electron is moving around the nucleus

in a well-defined orbit as in the Bohr model.

Q1: What is the wavelength of electromagnetic radiation that ejects 2.00-eV electrons from calcium
metal, given that the work function is 2.71 eV? What type of electromagnetic radiation is this?

Q2: An unknown elemental metal has work function of 8.01x10 -19 J. Upon illumination with UV light of
wavelength 162 nm, electrons are ejected with velocity of at 3.5 x 10 4 m/s. What is the threshold
wavelength? What is the work function in units of eV?

Q3: If the position of an electron is within the 10 pm interval, what is the uncertainty of the momentum?

Q4: If we know the velocity of an electron to within 3.5 x 10 7 m/s, then what is the uncertainty in its
position?
 Quantum Mechanics (Wave Mechanics)
To Schrödinger and de Broglie, the electron bound to the nucleus seemed similar to a standing wave, and they began
research on a wave mechanical description of the atom.

• The wave model was applied by de

Broglie to the Bohr atom by imagining
the electron in the hydrogen atom to be a
standing wave.

• Only certain circular orbits have a

circumference into which a whole number
of wavelengths of the standing electron
wave will “fit.”

• All other orbits would produce

destructive interference of the standing
electron wave and are not allowed.
Quantum Mechanics
Schrödinger: If electrons are waves, their
position and motion in space must obey a wave
equation.

Solutions of wave equations yield

wavefunctions, , which contain the
information required to describe ALL of the
properties of the wave.
 The Schrödinger Equation (1926)
• The central equation in Quantum Mechanics.
• Observable = total energy of system.

Schrödinger Equation Ĥψ Eψ Ĥ Operator

Hamiltonian

E Total Energy
where ˆ T
H ˆ V
ˆ and E = T + V.

• SE can be set up for any physical system.

• The form of Ĥ depends on the system.
• Solve SE   and corresponding E.
 Time-Dependent Schrodinger Wave Equation

Total E term K.E. term P.E. term

PHYSICS
NOTATION

Time-Independent Schrodinger Wave Equation

 Wavefunctions
• In QM, a “particle” is distributed in space like a wave.
• We cannot define a position for the particle.
• Instead we define a probability of finding the particle at any point in space.

• Wavefunction () – a wave representing the spatial distribution of a “particle”.

• Represents the amplitude of the still vaguely defined matter waves

• (x) – the magnitude of  at point x.

• Because  may be imaginary or complex  2 would be negative or complex.
• For the general case, where  is complex ( = a + ib) then:
2 = * where * is the complex conjugate of .
i 1
probability density
(* = a – ib)
 Particle Wavefunctions: Examples
Examples of (x)

y(x) y(x) y(x)

x x x

The corresponding probability distributions |(x)|2 of these states are:

|y|2 |y|2 |y|2

x x x
Key point: Particle cannot be associated with a specific location x.
 Probability distribution
Difference between classical and quantum cases
Classical Quantum
U(x U(x
) )

E E

x x
P(x
) P(x
)
=
y2

x x
 Wavefunctions

The Importance of 
•  completely defines the system (e.g. electron in an atom or molecule).
• If  is known, we can determine any observable property (e.g. energy, vibrational
frequencies, …) of the system.
• QM provides the tools to determine  computationally, to interpret  and to use  to
determine properties of the system.
 Wavefunctions
The Born Interpretation (1926)

“The square of the wavefunction at any point in space is proportional to the probability of finding the
particle at that point.”

Example: 1-D System

If the wavefunction at point x is (x), the probability of finding the particle in the
infinitesimally small region (dx) between x and x+dx is:

P(x)  (x)2 dx
 Normalization of the Wavefunction

P(r)  (r)2 d
• What is the proportionality constant?
• If  is such that the sum of (r)2 at all points in space = 1, then:
P(x) = (x)2 dx 1-D
P(r) = (r)2 d 3-D

• As summing over an infinite number of infinitesimal steps = integration, this means:

 2
Ptotal 1D   ψx  dx 1


 2    2
Ptotal 3D   ψr  dτ    ψx, y, z  dxdydz 1
 
• i.e. the probability that the particle is somewhere in space = 1.

• In this case,  is said to be a normalized wavefunction.

How to Normalize the Wavefunction

2
• If  is not normalized, then:
ψr  dτ A 1

• A corresponding normalized wavefunction ( Norm) can be defined:

1
ψ Norm r   ψr 
A

such that:
2

ψ Norm r  dτ 1
• The factor (1/A) is known as the normalization constant (sometimes represented by N).
 Hamiltonian Operator
• Wavefunction () contains all the information we need to know about any particular system.
• How do we determine  and use it to deduce properties of the system?
Operators and Observables
• If  is the wavefunction representing a system, we can write:
Q̂ψ Qψ

where Q – “observable” property of system (e.g. energy, momentum, dipole moment …)

Q̂ – operator corresponding to observable Q.

d/dx (eax) = a eax

d2/dx2 (sin ax) = a2 sin ax

^
𝑥 =𝑥
Operator for linear momentum in the x-direction: 𝜕
Operator for position in the x- ^𝑥=− 𝑖 ℏ
𝑝
direction is just multiplication by x 𝜕𝑥
Constructing Kinetic and Potential Energy QM Operators
1. Write down classical expression in terms of position and momentum.
2. Introduce QM operators for position and momentum.

Examples
1. Kinetic Energy Operator in 1-D T̂x
px2 ˆ ˆ x2
p  2 
d 2 
CMTx   QM Tx    
2m 2m 2m  dx 2 

2. KE Operator in 3-D
T̂ “del-squared”

2 2
p2 px  py  pz
2 ˆ2
ˆT  p  2   2 2 2 
   2

CM T  QM    2
2m 2m 2m 2m  x 2 y 2 z 2 
 2m

partial derivatives
3. Potential Energy Operator (a function of position) operate on (x,y,z)
V̂
 PE operator corresponds to multiplication by V(x), V(x,y,z) etc.
Examples

1. Particle Moving in 1-D (x)

ˆ ψ T
ˆ ψV
ˆ ψ Eψ  2   2 ψ 
H   Vx ψ Eψ
2m  x 2 
• The form of V(x) depends on the physical situation:
– Free particle V(x) = 0 for all x.
– Harmonic oscillator V(x) = ½kx2

2. Particle Moving in 3-D (x,y,z)

• SE   2   2 ψ  2 ψ  2 ψ 
    Vx, y, z ψ Eψ
2m  x 2 y 2 z 2 

or 2 2
  ψ  Vx, y, z ψ Eψ Note: The SE is a second
2m order differential equation
 Particle in a Box model
• Consider a particle with mass m that is free to
move back and forth along one dimension
between the values x = 0 and x = L.

• The potential energy V(x) of the particle is zero

at all points along its path, except at the
endpoints x = 0 and x = L, where V(x) is
infinitely large.

• Schrödinger equation contains the energy operator Ĥ.

• The potential energy is zero inside the box, the only energy possible is the kinetic energy of the
particle as it moves back and forth along the x axis.


 Particle in a Box model
• Each solution must be a function whose second derivative has the same form as the original
function.
• One function that behaves this way is the sine function.
  2   2 ψ 
 Eψ
2m  x 2 
• This is a second order differential equation – with general solutions of the form:
 = A sin kx + B cos kx

 2ψ 
   k 2 A sin kx  B cos kx   k 2 ψ
 x 2 
 

• SE 
 2   2 ψ    2 
  
2m  x 2   2m 
  k 
2
ψ Eψ

 2 2 (i.e. E depends on k).

k 
E
2m
Restrictions on 

• In principle Schrödinger Eqn. has an infinite number of solutions.

• So far we have general solutions:

– any value of {A, B, k}  any value of {,E}.

• BUT – due to the Born interpretation of , only certain values of  are physically acceptable:

– outside box (x<0, x>L) V =   impossible for particle

to be outside the box
 2 = 0   = 0 outside box.
–  must be a continuous function
 Boundary Conditions  = 0 at x = 0
 = 0 at x = L.
Effect of Boundary Conditions

1. x = 0  = A sin kx + B cos kx = B
0 1
=0 B=0
  = A sin kx for all x

2. x = L  = A sin kL = 0

A=0 ?  sin kL = 0 ? 
(or  = 0 for all x)
sin kL = 0  kL = n n = 1, 2, 3, …
(n  0, or  = 0 for
all x)
Allowed Wavefunctions and Energies

• k is restricted to a discrete set of values: k = n/L

• Allowed wavefunctions: n = A sin(nx/L)

• A = (2/L)  2  nx 
Normalization: ψn  L
sin  
 L 
Allowed Wavefunctions and Energies

• 2  nx 
Normalization: A = (2/L)  ψn  L
sin  
 L 

• Allowed energies: k 2 2 n 2 π 2 2
En  
2m 2mL2

 n 2h2
En 
8mL2
The application of the boundary conditions has led to a series
of quantized energy levels. That is, only certain energies are
allowed for the particle bound in the box.
Quantum Numbers

• There is a discrete energy state (En), corresponding to a discrete

wavefunction (n), for each integer value of n.

• Quantization – occurs due to boundary conditions and requirement

for  to be physically reasonable (Born interpretation).

• n is a Quantum Number – labels each allowed state (n) of the

system and determines its energy (En).

• Knowing n, we can calculate n and En.

Properties of the Wavefunction
2 nx 
• Wavefunctions are standing waves: ψn  L
sin  
 L 

• The first 5 normalized wavefunctions for the particle in the 1-D box:

• Successive functions possess one more half-wave ( they have a shorter wavelength).

• Nodes in the wavefunction – points at which n = 0 (excluding the ends which are constrained to be
zero).

• Number of nodes = (n-1) 1  0; 2  1; 3  2 …

 n 2h2
Energies En 
8mL2

• En  n2/L2  En as n (more nodes in n)

En as L (shorter box)
n (or L)  curvature of n
 KE  En

E  E
2 node

L
1

L1 L2
• En  n2  energy levels get further apart as n
n E
9h 2
3 E3 
8mL2

4h 2
2 E2 
8mL2

h2
1 E1  2 h2
8mL ZPE 
0 8mL2

• Zero-Point Energy (ZPE) – lowest energy of particle in box:

h2
ZPE E min E 1 
8mL2
• CM Emin = 0
• QM E = 0 corresponds to  = 0 everywhere (forbidden).
Density Distribution of the Particle in the 1-D Box

• The probability of finding the particle between x and x+dx (in the state represented by
n) is:
Pn(x) = n(x)2 dx = (n(x))2 dx (n is real)

 nx 
 Pn x   L2 sin 2   dx
 L 

• Note: probability is not uniform

– n2 = 0 at walls (x = 0, L) for all n.
– n2 = 0 at nodes (where n = 0).
Assume that an electron is confined to a one-dimensional box 1.50 nm in length. Calculate the lowest three energy
levels for this electron, and calculate the wavelength of light necessary to promote the electron from the ground state
to the first excited state.
Particle in a 2-D Square or 3-D Cubic Box
• Similar to 1-D case, but   (x,y) or (x,y,z).
• Solutions are now defined by 2 or 3 quantum numbers

e.g. [n,m, En,m]; [n,m,l, En,m,l].

• Wavefunctions can be represented as contour plots in 2-D
 Hydrogen Atom

• The series of atoms/ions H, He+, Li2+, Be3+ …

all have: 1 electron (charge –e)
nucleus (charge +Ze)

• To determine the electronic wavefunction (  = e) and allowed electronic energy levels (E), we
must set up and solve the Schrödinger Equation for a single electron in an atom.

-e
me
+Ze
mN
• Consider 3-D motion of the electron (-e) relative to the nucleus (+Ze):

Hamiltonian Operator ˆ T
H ˆ V
ˆ

2 2 m e m N
Kinetic Energy
T̂   where  m e
2 me  m N
2
Potential Energy ˆ Vr    Ze where
V r  x2  y2  z2
4 0 r
(electrostatic attraction between electron and nucleus).

-e
  2
 2 2  me
2  2  2  2  r
 x y z 
  +Ze
mN
• We must solve the 2nd order differential equation:
2 2
  ψ  Vr ψ Eψ
2
• Because of the spherical symmetry of the atom, it is convenient to describe the position of the electron in spherical
polar coordinates (r,,), rather than Cartesians (x,y,z).
The Schrödinger Equation in Spherical
Coordinates

•The wave function y is a function of r, q, f. This is a potentially complicated function.

•Assume instead that y is separable, that is, a product of three functions, each of one variable only:
• Due to this spherical symmetry, the wavefunction can be separated into a product of radial and angular
components:
(r,,) = R(r).Y(,)

• Imposing boundary conditions  3 quantum numbers (n, , m)

 n,,m(r,,) = Rn,(r).Y,m(,)
angular
radial
wavefunction
wavefunction
(spherical harmonic)
Quantum Numbers

n,,m(r,,) = Rn,(r).Y,m(,)

•  depends on 3 quantum numbers (n, , m).

1. Principal Quantum Number (n)

• Positive integer n = 1, 2, 3 …
• For H and 1-e ions, the electron energy depends only on n

 e 4   Z2 
E n   2 2   
 8h    n2 
 0   
2. Orbital Angular Momentum Quantum Number ()
• For a given value of n,  can take the integer values:
 = 0, 1, 2 … (n-1)
e.g. n=1 =0
n=2  = 0, 1
n=3  = 0, 1, 2

3. Orbital Magnetic Quantum Number (m)

• For a given value of , m can take the integer values:

m = 0, 1, 2 …  

e.g. =0 m = 0
=1 m = 0, 1

• There are (2+1) allowed values of m.

Atomic Orbitals
• The wavefunctions (n,,m) describing an electron in an atom are known as atomic
orbitals.

• Each atomic orbital (1-e wavefunction) is uniquely defined by 3 quantum numbers

(n,,m).

• The orbital () gives the spatial distribution of the electron (via the Born
interpretation of ||2).

• Orbitals are often drawn as 3-D surfaces which enclose approx. 90% of the probability
of finding the electron.
 Quantum Numbers and Atomic Orbitals

• Orbitals differ from each other in size, shape and orientation:

– the orbital size is defined by the principle quantum number n

– the type of orbital (it’s shape) is defined by the angular momentum quantum number 

– the orientation of the orbital is defined by the orbital magnetic quantum number m
 Shape of Atomic Orbitals
Shape – determined by the angular wavefunction Y,m(,)

1s orbital (n = 1,  = 0)
32
1  1 
• Normalized wavefunction:  1s   


 e  r a0
  a0 
• Has no angular dependence
(spherically symmetric, depends only on r).
+
• All s orbitals are spherically symmetrical.

2s orbital ns orbital

2s   2  r e  r 2 ns   f r e  r n
• As n, orbitals expand – average radius r
2p orbitals (n = 2,  = 1)

• There are 3 degenerate orbitals, with 3 different m values

(0,1).

• e.g. m = 0  2pz orbital (pointing along z-axis)

52
 2p z  
1  1


 rcos e  r 2a 0
+ -

4 2  a 0

 - +

• m = 1  2px, 2py orbitals -

+
Atomic Orbitals

The p orbitals:

Three orientations:
l = 1 (as required for a p orbital)
ml = –1, 0, +1
Atomic Orbitals

The d orbitals:

Five orientations:
l = 2 (as required for a d orbital)
ml = –2, –1, 0, +1, +2
Electronic Shells, Sub-shells and Orbitals
• All orbitals with the same value of n together constitute an electronic shell.

n 1 2 3 4
Shell K L M N
• For each n, orbitals with the same value of  together constitute an electronic sub-shell.

• Each sub-shell consists of (2+1) orbitals, each with a different m value.

 0 1 2 3
Sub-shell s p d f
No. orbitals 1 3 5 7
• Possible combinations of shells and sub-shells.

 0 1 2 3 …
n
1 1s
2 2s 2p
3 3s 3p 3d
4 4s 4p 4d 4f
…

• Total number of orbitals in shell n is n2.

 Electronic Shells, Sub-shells and
Orbitals

3d orbitals
l=2 ml =2 ml =1 ml =0 ml =1 ml =2

n=3
3p orbitals
l=1 ml =1 ml =0 ml =1

3s orbital
l=0 ml =0

shell sub-shells orbitals

 Atomic Orbital Energy Diagram for H

• Orbital energies depend only on the principal quantum

number n.

• For a given n value (shell), all sub-shells () and orbitals

(m) have the same energy
– i.e. they are degenerate.
 Electron Spin
• Stern and Gerlach (1921) observed that a beam of Ag atoms is split into 2 beams by an
inhomogeneous magnetic field.

• Dirac (1930) introduced relativistic effects into Quantum Mechanics and showed that to
completely describe the state of an electron we must specify:
1. The orbital (n,,m)
2. The spin state of the electron

• Electron spin is characterised by 2 quantum numbers:

– spin angular momentum q. no. s ( = ½ for all electrons)
– spin magnetic q. no. ms ( = ½).
• Spin angular momentum (S) has magnitude:

3
S  ss  1 
2
• The projection of S on the z-axis:
Sz = ms = ½ 

• There are two possible electron spin states:

ms = +½ “spin up” 
ms = -½ “spin down” 

• Spin is an intrinsic property of the electron and is not connected with orbital motion.

• Complete specification of an electron in an atom requires 4 quantum numbers (n,,m,ms) – as s is

fixed.
 The fourth quantum number: Electron Spin

ms = +1/2 (spin up) or -1/2 (spin down)

Spin is a fundamental property of electrons, like its charge and mass.

Quantum Numbers (QN)

Principal QN:

n = 1, 2, 3, 4……

Angular momentum QN:

l = 0, 1, 2, 3…. (n -1)

Rule: l = (n - 1)

Magnetic QN:

ml = …-2, -1, 0, 1, 2, ..

Rule: -l….0….+l
 Many-Electron Atoms
• For atoms with 2 or more electrons, the Schrödinger Eqn. must include KE terms for all electrons
and PE terms for all e-e and e-n interactions.

• Example: He (2 electrons)
T̂ in
2 terms
3 terms in
V̂
-e(1)
r1
r12
Z = +2e -e(2)
S.E. r2
2 2 2 
 2e 2 2e 2 e2 
 2
1  2        E
 
2m e 2m e  4 0 r1 4 0 r2 4 0 r12 
where
 2 2 2 
i2  2  2  2 
 x y i z i 
 i
• For N electrons: N = (r1,r2,r3 … rN)

• For more than 1 e, S.E. cannot be solved analytically – though good numerical
solutions may be obtained from computer calculations.

 Approximations must be made.

The Orbital Approximation

• The total wavefunction (N) for the N-electron atom is approximated by the
product of N 1-e orbitals similar to those of hydrogenic ions:

N = (r1,r2,r3 … rN) = (r1)(r2)(r3)…(rN)

 Bonding in Molecules
Exact solution of the Schrödinger Equation is not possible for any molecule – even the simplest
molecule H2+.
e
rA rB

HA RAB HB

Full Hamiltonian operator for H2+ :

KE PE

 
2 2 2
ˆ   2 2  2 e  1 1  e2
H A  B  e     
2m p 2m e 4 0  rA rB  4 0 R AB
nuclear K.E. electron K.E. e-n attraction n-n repulsion
 Application
• Computational chemistry is a rapidly growing field in chemistry.
• Computers are getting faster.
• Algorithms and programs are maturing.

• Some of the almost limitless properties that can be calculated with computational
chemistry are:
• Equilibrium and transition-state structures
• dipole and quadrupole moments and polarizabilities
• Vibrational frequencies, IR and Raman Spectra
• NMR spectra
• Electronic excitations and UV spectra
• Reaction rates and cross sections
• thermochemical data
 Limitations
• Schrödinger Equation can only be solved exactly for simple systems.
• Rigid Rotor, Harmonic Oscillator, Particle in a Box, Hydrogen Atom

• For more complex systems (i.e. many electron atoms/molecules) we need to make some
simplifying assumptions/approximations and solve it numerically.

• However, it is still possible to get very accurate results (and also get very crummy
results).
• In general, the “cost” of the calculation increases with the accuracy of the calculation and the size of the
system.
Yttrium catalyzed rearrangement of acetylene
40

2
A
20

Energy (kcal/mol) 2
A’
0

2
B2
-20
2
A1
2
B2 2
A’ 2
A2 2

B
-40
2
A1 2

-60

Reaction Coordinate
Biochemistry applications
 Tools
• There exist a large number of software packages capable of performing
electronic structure calculations.
• MOLPRO, GAMESS, COLUMBUS, NWCHEM, MOLFDIR, ACESII, GAUSSIAN, ...

• The different programs have various advantages and capabilities.

• We also have available to us Gaussview which is a GUI that interfaces with

Gaussian for aiding in building molecules and viewing output.