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CHEM F111 General Chemistry Lecture 01

Quantum Theory - Origins
(Classical) mechanics – Developments
by early 19th Century
Sir Issac Newton (1642-1726)

Newtonian Mechanics
(17th century and beyond)
Joseph Louis Lagrange (1736-1813)

Sir William Rowan Hamilton (1805-1865)
Lagrangian Mechanics (1788)
Hamiltonian Mechanics (1833)
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Some developments in physics from the
19th century
John Dalton – Concept of atoms (1803)
Amedeo Avogadro – Concept of molecules (1811)
Sir J. J. Thomson – Concept of electron (1897)
Millikan – Charge of elementary particles (1909)

Objectives and outcome of learning
In the light of the topics:

●
Black-body radiation
●
Photo-electric effect
●
Atomic emission spectrum of hydrogen
we will learn that

●
Classical physics fails to describe certain experimental
observations
●
Satisfactory explanation to the observed phenomena can
only be possible by introduction of quantization

Black-body radiation
Perfectly black-body: A body that absorbs and emits radiations of all

frequencies
Black-body when sufficiently hot relative to the surrounding emits
electromagnetic radiations of various frequencies
Was first studied in late 19th century
●
William Herschel (1800) thermal radiation
●
Balfour Stewart (1858) compared the radiations from lamp-black with
radiations from non-black bodies
●
Gustav Kirchoff (1859) independently discovered Stewart’s finding and
expanded further to his theory of thermal emission
●
Lummer and Pringsheim (1899) plotted the dependence of intensity
(energy density, emissive power) with radiation wavelength/frequency and
temperature
●
Planck (1900) successfully explained the behavior of BBR using his
quantum hypothesis
Black-body radiation (BBR)
• Heated body emits radiation. The energy emitted per unit area per second,
called the emissive power, is a function of the wavelength (or frequency),
and temperature
• Black body – one which absorbs all the radiation that falls on it (and emits
it all back when sufficiently hot)
• Let J(λ, T) be the emissive power of a black body.
What is the form of J(λ, T)?

BBR: Experimental findings by Lummer
and Pringsheim (1899)
• Conveniently studied by analyzing the radiation energy density in cavity
whose walls are at T
• Can show that the energy density ρ(λ,T) = J(λ,T)/c
• ρ(λ,T)dλ is the energy per unit volume associated with energy of radiation
of wavelength λ to λ+dλ
• Maximum in ρ(λ,T), position of maximum shifts to lower wavelength
(higher frequency) with increasing temperature

BBR: Verifiable observations
Emittance M: Total power emitted per unit area

M = σT4, (Stefan-Boltzmann law);
where, σ=5.67×10-8 Wm-2K-4; (Stefan-Boltzmann constant)
Weins’ displacement law:

λmaxT = 2.9 mm·K OR νmax/T = αk/h (where α≈2.821439…)

BBR: Failed attempts in explaining the
trends
Why does the curve go through a maximum?
Attempts to explain BBR:

●
Rayleigh and Jeans pictured the radiation energy in the cavity as a collection of
oscillators. Using the classical physics and empirical observations, they derived the
formula:
8πk T
ρ(λ , T )d λ= 4
dλ
λ
Does well at long wavelength (low frequency), but fails miserably at short
wavelengths (ultraviolet catastrophe)
●
Wien, in his formulation guessed the qualitative trend at short wavelengths (high
frequencies), but failed quantitatively at long wavelengths.
e−β c /λ T
ρ(λ , T )d λ ∝ 5
dλ
λ

BBR: Planck’s quantum hypothesis
explained it all
Assumption: Molecules of the black-body behave like simple harmonic oscillators
and have characteristic vibrational frequency
Crucial assumption: The energy exchange between the walls of the black-body and
the interior could only occur in integral multiples of a quantum of energy.
Δ E=n h ν ; n=0,1,2,…; ν=c /λ
Using this, Planck derived radiation formula:
8πhc dλ
ρ(λ , T )d λ= ( λ 5 )
e h c /λ kT
−1
; where, k is the Boltzmann constant.
Planck found that with h=6.626 x 10-34Js,

Js the above expression gives perfect
agreement with experiment
●
Reduces to Rayleigh and Jeans law at larger wavelengths (lower frequencies)
●
Reduces to Wein’s formula at shorter wavelengths (higher frequencies)
●
Differentiate in order to get Wein’s displacement law
●
Integrate in order to get Stefan-Boltzmann law

BBR: Planck’s quantum hypothesis
explained it all
8πhc dλ
ρ(λ , T )d λ=( )
λ 5 e h c /λ kT −1
DIY: Plot the energy density as a function of wavelength for different

values of temperature, using libreoffice calc or msoffice excel or any
graph plotting software available with you.
Set all the constants in the expression to unity for your convenience.

The photo-electric effect
• Threshold frequency ν0 characteristic of the metal below which there

is no emission
• The kinetic energy of the emitted electrons increases linearly with the
frequency of the incident radiation, but is independent of the incident
intensity
●
For frequency above the threshold, even at very low intensity, the
emission is instantaneous
●
Photoelectric current is proportional to the intensity, but not dependent
on frequency
Einstein proposed particle nature of light
and explained the photoelectric effect
●
Einstein postulated that light may be
considered as a collection of particles, each of
energy hν
●
Kinetic energy of emitted electrons is given by
K = hν – φ, where the work function φ is the
energy required to just overcome the binding
energy of the electron, and with φ = hν0, (ν0 is
threshold frequency) one obtains K = hν – hν0
Intensity being proportional to the number of photons cannot bring about

photoelectric effect if the frequency is less than the threshold frequency.
Photoelectric current is proportional to number of photoelectrons, which is in
turn proportional to intensity.
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Foundations of Quantum Mechanics
Review of lecture 01
• Planck black body radiation

• Photoelectric effect – Einstein’s explanation
Click to edit Master subtitle style
8/16/23
Emission spectrum of hydrogen atom –
discrete lines observed
When the electron in the hydrogen atom undergoes a transition from energy level
E2 to E1, the transition is accompanied by the emission of a photon of frequency
ν = (E2 – E1)/h, or in terms of the wave number
ṽ = 1/λ = (E2 – E1)/hc = R(1/n12 – 1/n22)
Lyman, Balmer, Paschen, Brackett, Pfund series!

Bohr’s model of hydrogen atom
explained the line spectrum
• Electron (mass m and charge –e)

–e moving in circular orbit of radius r about
nucleus of charge Ze
mv2/r = Ze2/4πε0r2
•According to classical physics, electron must radiate energy, and fall into the
nucleus
• Bohr postulated stable orbits with radius given by mvr = nh/2π = nħ,
nħ
n=1,2,3,… - quantization of angular momentum
• Combining, one finds r = (n2/Z)a0, where
a0 = 4πε0ħ2/me2 is the Bohr radius
• Also the energy E = p2/2m – Ze2/4πε0r = – Ze2/8πε0r
En = -mZ2e4/32π2ε02ħ2n2 = -RhcZ2/n2 where R is the Rydberg constant

Failures of classical physics
In Classical Physics,
•Any kind of motion can be excited to any arbitrary value of the

energy
• A particle travels in a trajectory, a path with a precisely defined
position and momentum at each instant
• Waves and particles are distinct concepts
These are excellent approximations at the macroscopic level, but
break down when one considers the behavior of microscopic
entities such as electrons, atoms, molecules etc.
8/16/23
Louis Victor de Broglie
French Physicist
Born:
August 15, 1892
Died:
March 19, 1987
8/16/23
de Broglie matter waves
●
If light (radiation) can be viewed as a collection of particles, then
can entities considered as particles also be seen as waves?
●
For photons, using pc = E = hc/λ, one can solve for the momentum
of a photon: p = h/λ
●
de Broglie postulated the existence of matter waves associated
with particles, with a wave length given by λ = h/p,
h/p where p is the
linear momentum
8/16/23
Electron diffraction
Davisson and Germer performed electron diffraction

experiment in 1923-1927 and found that the electrons
obeyed Bragg's law confirming the wave nature of
electrons.
Clinton Joseph Davisson (left) and

Lester Germer (right)
8/16/23
de Broglie matter waves
Macroscopic objects are so massive that the de Broglie

wavelengths are tiny, and lead to no observable consequences
8/16/23
Wave – Particle Duality
Homework: Use de Broglie hypothesis to justify the Bohr's

assumption of stable orbits of electron in hydrogen-like atoms.
Are electrons, protons, atoms, photons etc., particles or waves?
The answer is ‘neither’ or ‘both’. Whether the ‘particle’ or ‘wave’
aspect or behavior is observed depends on the nature of the
measurement being made. The two are complementary.
8/16/23
Two slit experiment

Experiment with Bullets:
Arrive in identical discrete lumps – particles
Distribution with both slits open is the sum of that with slit 1 alone open
and that with slit 2 alone open; no interference.
8/16/23
Two slit experiment
Experiment
Clickwith water
to edit waves:
Master subtitle style
Intensity can be varied by changing amplitude of source (Intensity
proportional to square of amplitude); no lumps.
Intensities don’t add, the amplitudes do – there is interference -
waves
8/16/23
Two slit experiment
Experiment with electrons, photons etc. :

Arrive in identical lumps – particles, but the distribution shows
interference – waves
8/16/23
Probabilities and amplitudes
System has a dual potential nature, but the observed nature is particle-like or
●
wave-like, depending on the nature of the observation

Does the electron pass through hole 1 or hole 2? Question needs to be
●
answered only if the experiment being performed is capable of answering. If

yes, then the interference will be lost.
●
Can one determine the momentum of the electron? Yes, if the experiment is
devised to study the interference pattern; however, then the position would
become uncertain.
8/16/23
Werner Heisenberg
German Physicist
Born:
December 05, 1901
Died:
February 01, 1976
8/16/23
Heisenberg’s Uncertainty Principle
Heisenberg’s uncertainty principle is the consequence

of wave-particle duality.
The uncertainty principle emerged in the context of
matrix mechanics, developed by Heisenberg, when he
was working at the Neils Bohr’s institute (1925~27).
The uncertainty principle (as originally presented by Heisenberg in 1927)
states that the more precisely the position of some particle is determined,
the less precisely its momentum can be predicted from initial conditions,
and vice versa.
The formal inequality was derived later, by Kennard and Weyl, in which
the standard deviation in the measurement of a quantity was referred to as
‘uncertainty’ in its measurement.
ℏ ℏ ℏ
Δ p x Δ x≥ Δ p y Δ y≥ Δ p z Δ z≥
2 2 2
8/16/23
Heisenberg’s Uncertainty Principle
It is impossible to specify simultaneously, with arbitrary precision, (a given

Cartesian component of) the momentum and position of a particle
ℏ ℏ ℏ
Δ p x Δ x≥ Δ p y Δ y≥ Δ p z Δ z≥
2 2 2
More generally, it is impossible to specify simultaneously, with an arbitrary
precision, the canonically conjugate variables in quantum mechanics.
Canonically conjugate variables are the physically measurable quantities, which
when multiplied have the dimensions as that of ħ.
For example,
●
Any (even non-cartesian) component of position and the conjugate momentum
●
Angular position and angular momentum
●
Energy and time
For energy time uncertainty measurement, the inequality is slightly different:
Δ E Δ t ≥ℏ
8/16/23
Uncertainty Principle
Definite wavelength → definite momentum, but since wave

extends over all space, no information on position
8/16/23
Superposition – Fourier synthesis
Superposition of waves, uncertainty in both position and

momentum
8/16/23
Uncertainty Principle
Particle with precisely defined position/ Wavelength

undefined, no information on momentum
8/16/23
BITS Pilani
Pilani Campus

Wave-equation, wavefunction, operators and
quantum description of simple systems
• Wave-particle duality
• Uncertainty principle

Uncertainty principle: Consequences
•Impossible to exactly and simultaneously measure position and

momentum or energy and time (or, in general, any pair of
canonically conjugate quantities, e.g. angular momentum, angular
position, etc)
•Impossible to get trajectories, equations of motion, etc
•If both position as well as momentum (or energy-time, etc) are
measured, there always lies uncertainty in measurement of both
and one needs to work within probabilistic regime.
•Only way to get meaningful insight is to learn the mathematical
form describing the wave nature of the system

Wavefunction Ψ/ψ (PSI/psi)
Example – One dimensional one-particle system

Consider the following plot of the wavefunction:
The particle is confined to the region where the wavefunction is

non-zero.
What are the most-probable positions of the particle?



non-zero.
Recall – intensity is proportional to the square of the amplitude


non-zero.
Recall – intensity is proportional to the square of the amplitude
When scaled properly*, the area under the

Ψ2 curve gives the total probability of
finding the particle in that region at that
instant. Area under any part of the curve
would resemble with partial probability at
the given instant.
(Born interpretation)
The wavefunction, for M-particle N-dimensional system is function of M×N

position variables and the time.
For example, the wavefunction of a 2-particle 3D system can be expressed
as Ψ(x1,y1,z1,x2,y2,z2, t) in Cartesian coordinates.
In general, the wavefunction could be complex. Hence, instead of squaring
the wavefunction, its complex conjugate is used for obtaining probability
density.

Probability versus probability density
In a one-particle 1D system, |Ψ(x,t)|2 multiplied by dx gives the instantaneous

probability of finding the particle in the given infinitesimal length. In a one-
particle 3D system, |Ψ(x,y,z,t)|2 multiplied by the volume element dV=dxdydz
gives the instantaneous probability of finding the particle in the given
infinitesimal volume.
In a general for M-particle system in N-dimensional Euclidean space, this can
be appropriately generalized. We denote the general volume element as dτ ,
hereafter.
Thus, in general, when scaled properly*, the quantity, |Ψ(x,y,z,t)|2dτ, represents
probability, whereas the quantity, |Ψ(x,y,z,t)|2, represents the probability
density. (Scaling of the wavefunction – the normalization …. to be discussed later)
Max Born
British Physicist
Born:
December 11, 1882
Died:
January 05, 1970

The state of a quantum-mechanical system (one particle system) is

completely specified by a function Ψ(x,y,z,t), that depends on the
coordinates of the particle and on the time. This function, known as the
wavefunction of the system, has important property that Ψ2dτ (more
generally |Ψ|2dτ, represents the probability that the particle is located in
the infinitesimal element of volume dτ located about the given point
(x,y,z), at the instant, t.
(Born interpretation) (Postulate 1 of Q.M.)
(For multi-particle multi-dimensional system, this can be appropriately

extended: The wavefunction would be Ψ(x1,….zN,t) and the general
volume element would be dτ=dx1dy1dz1….dxNdyNdzN.)
Probability Density
Probability density
│ψ│2 is a physically
meaningful quantity

Erwin Schrödinger
Austrian Physicist
Born:
August 12, 1887
Died:
January 04, 1961

Wave function (Example: 1D free particle)
Consider a particle moving along a positive x-direction.

The wave associated with the particle must be a well-behaved simple
harmonic wave of the form:
Ψ ( x ,t )= A e
i( κ x−ω t ) (κ is propagation constant)


Ψ ( x ,t )= A e
We have:
h h h 2π
E=h ν= ⋅2 π ν=ℏ ω p x = = ⋅ =ℏ κ
2π λ 2π λ


Ψ ( x ,t )= A e
We have:
h h h 2π
E=h ν= ⋅2 π ν=ℏ ω p x = = ⋅ =ℏ κ
2π λ 2π λ
It follows,
i
ℏ ( p x⋅x−E⋅t )
Ψ ( x ,t )= A e

We have obtained: i
Ψ ( x ,t )= A e

We have obtained: i
Ψ ( x ,t )= A e
We now study the spatial dependence of the function:

i
∂ Ψ = A e ℏ ( p ⋅x− E⋅t ) i p = i p Ψ
x
∂x ℏ x ℏ x

We have obtained: i
Ψ ( x ,t )= A e

i
∂ Ψ = A e ℏ ( p ⋅x− E⋅t ) i p = i p Ψ
x
^
p Ψ=
ℏ ∂
Ψ
∂x ℏ x ℏ x x
i ∂x

We have obtained: i
Ψ ( x ,t )= A e

i
∂ Ψ = A e ℏ ( p ⋅x− E⋅t ) i p = i p Ψ
x
^
p Ψ=
ℏ ∂
Ψ
∂x ℏ x ℏ x x
i ∂x
ℏ ∂
^
px = (Momentum Operator defined)
i ∂x

We have obtained: i
Ψ ( x ,t )= A e

i
∂ Ψ = A e ℏ ( p ⋅x− E⋅t ) i p = i p Ψ
x
p^ Ψ=
ℏ ∂
Ψ
∂x ℏ x ℏ x x
i ∂x
ℏ ∂
^
i ∂x
Taking the second derivative wrt x, it follows
2
2
∂ Ψ =− x Ψ p 2 2 ∂
2
2 2
p x Ψ=−ℏ 2
Ψ
∂x ℏ ∂x

We have obtained: i
Ψ ( x ,t )= A e

i
∂ Ψ = A e ℏ ( p ⋅x− E⋅t ) i p = i p Ψ
x
p^ Ψ=
ℏ ∂
Ψ
∂x ℏ x ℏ x x
i ∂x
ℏ ∂
^
i ∂x
2
2
∂ Ψ =− x Ψ p 2 2 ∂
2
2 2
p x Ψ=−ℏ 2
Ψ
∂x ℏ ∂x
Consequently, we have
p2x 2
ℏ ∂2
=− (K.E. Operator defined)
2m 2 m ∂ x2

We have obtained: i
Ψ ( x ,t )= A e
Next, we study the temporal dependence of the function:

i
∂Ψ =A e ℏ ( p x⋅x− E⋅t ) −i 1
ℏ E= EΨ
∂t iℏ

We have obtained: i
Ψ ( x ,t )= A e

i
∂Ψ =A e −i
ℏ ( p x⋅x− E⋅t )
E=
1
E Ψ ^ Ψ=i ℏ ∂ Ψ
E
∂t ℏ iℏ ∂t
^ ℏ ∂
E=i (Total energy operator*)
∂t

We have obtained: i
Ψ ( x ,t )= A e

i
∂Ψ =A e −i
ℏ ( p x⋅x− E⋅t )
E=
1
E
∂t ℏ iℏ ∂t
^ ℏ ∂
∂t
Let V(x) be the potential energy operator.
ℏ2 ∂ 2 Ψ ^ ∂Ψ
It then follows: − 2 m 2
+ V ( x ) Ψ =i ℏ
∂t
∂x

We have obtained: i
Ψ ( x ,t )= A e

i
∂Ψ =A e −i
ℏ ( p x⋅x− E⋅t )
E=
1
E
∂t ℏ iℏ ∂t
^ ℏ ∂
∂t
ℏ2 ∂ 2 Ψ ^ ∂Ψ
It then follows: − 2 m 2
+ V ( x ) Ψ =i ℏ
∂t
∂x
^ Ψ = i ℏ ∂ Ψ (Time-dependent Schrödinger equation)

H
∂t
The time dependent Schrödinger equation describes time evolution of the
system
Postulates of quantum mechanics
Postulate 1:
The state of a quantum-mechanical system is completely specified by a

function Ψ(x1,y1,z1,….xN,yN,zN, t),
t) that depends on the coordinates of all the
particles and on the time. This function, known as the wavefunction of the
system, has important property that |Ψ|2dτ=(Ψ
τ= *Ψ)dτ, (where,
dτ=dx1dy1dz1...dxNdyNdzN) represents the probability that the particle 1 is
in volume element dx1dy1dz1 surrounding (x1,y1,z1), particle 2 is in the
volume dx2dy2dz2 surrounding (x2,y2,z2), and so on, at the instant, t.

Postulate 2:
To every observable in classical mechanics, there corresponds an
operator in quantum mechanics.
Postulate 5:
The wavefunction of a system evolves in time according to the time-
dependent Schrödinger equation.

BITS Pilani
Pilani Campus

Wave-equation, wavefunction, operators and
quantum description of simple systems
• Wave-particle duality; Uncertainty principle

• Wavefunction – definition and interpretation
• Time-dependent Schrödinger equation

(revision)
Postulate 1:
The state of a quantum-mechanical system is completely specified by a

function Ψ(x1,y1,z1,….xN,yN,zN, t),
t) that depends on the coordinates of all the
particles and on the time. This function, known as the wavefunction of the
system, has important property that |Ψ|2dτ=(Ψ
τ= *Ψ)dτ, (where,
dτ=dx1dy1dz1...dxNdyNdzN) represents the probability that the particle 1 is
in volume element dx1dy1dz1 surrounding (x1,y1,z1), particle 2 is in the
volume dx2dy2dz2 surrounding (x2,y2,z2), and so on, at the instant, t.

(revision)
Postulate 2:
To every observable in classical mechanics, there corresponds an
operator in quantum mechanics.
Postulate 5:
The wavefunction of a system evolves in time according to the time-
dependent Schrödinger equation.

Wavefunction: one-particle system in 1D
(revision)
We have obtained: i
Ψ ( x ,t )= A e

i
∂ Ψ = A e ℏ ( p ⋅x− E⋅t ) i p = i p Ψ
x
p^ Ψ=
ℏ ∂
Ψ
∂x ℏ x ℏ x x
i ∂x
ℏ ∂
^
i ∂x
2
2
∂ Ψ =− x Ψ p 2 2 ∂
2
2 2
p x Ψ=−ℏ 2
Ψ
∂x ℏ ∂x
p2x 2
ℏ ∂2
=− (K.E. Operator defined)
2m 2 m ∂ x2

Wavefunction: one-particle system in 1D
(revision)
We have obtained: i
Ψ ( x ,t )= A e
i
∂ Ψ = A e ℏ ( p ⋅x− E⋅t ) −i E= 1 E Ψ
x
^ Ψ=i ℏ ∂ Ψ
E
∂t ℏ iℏ ∂t
^ ℏ ∂
∂t
2
It then follows: − ℏ ∂ 2
Ψ + V^ ( x ) Ψ =i ℏ ∂ Ψ
2 m ∂ x2 ∂t
H^ Ψ = i ℏ ∂ Ψ (Time-dependent Schrödinger equation)
∂t
The time dependent Schrödinger equation describes time evolution of the

system
Variable separation
(one particle system in 1D)
2 2
We have − ℏ ∂ Ψ ( x ,t ) ^ ∂ Ψ ( x ,t )
+ V ( x ) Ψ ( x , t )=i ℏ
2m ∂x
2
∂t
Suppose it is possible to express the wavefunction as Ψ ( x ,t )=ψ( x) ϕ(t )
Then, by variable separation method, one can solve and obtain
2 2
H^ ψ= E ψ , that is : − ℏ d ψ ^
+ V ( x) ψ=E ψ
2 m dx 2
This is (1D) time-independent Schrödinger equation. (Note that this is
possible because the Hamiltonian operator is time-independent in this case).
dϕ
The time-dependent part gives: i ℏ =E ϕ ⇒ ϕ (t )=e−iEt /ℏ
dt
What will be the probability density in such a case?
|Ψ ( x , t )|2 =Ψ ( x ,t )∗ Ψ ( x , t )
=ψ ( x)∗ ψ( x) ϕ(t )∗ ϕ (t )=ψ( x)∗ ψ( x) eiEt / ℏ e−iEt /ℏ =|ψ( x)|2
The probability density (and hence, the probability) turns out to be time-
independent! Such a state is said to be a stationary state.
Probability Density
Probability
density │ψ │2
is physically
significant

Normalization
• The total probability of finding the system (particle) in space is

obtained by integrating the probability density over the volume
element, spanning the volume enclosed by the boundaries.
∞
• Total probability
∫
−∞
∗
Ψ Ψ d τ=N
• The value of N should be positive definite, so that Ψ can be scaled

by a factor of N-1/2, so that the total probability is scaled to unity.
This procedure of scaling is known as normalization.

Well-behaved wavefunction
A function is said to be well-behaved when it satisfies following

conditions:
• The wavefunction should be finite and single-valued.

• The wavefunction and its first derivative should be continuous
everywhere.
• The wavefunction and its first derivative should be differentiable
everywhere (except maybe at a point where the potential goes to
infinity).
• The wavefunction should die at boundaries.
• The wavefunction should be quadratically integrable
(normalizable).

Operators
Operator is a mathematical instruction or rule that when acts on a

function, transforms it to another function.
e.g. let an operator A be “derivative wrt x” operator. Then,
A f(x) = g(x); where g(x)= df/dx
Multiplicative operators simply multiply the function e.g. position
operator, potential energy operator, etc.
Operators can have more complicated form (e.g. sum of two or more
operators – e.g. Hamiltonian operator)

Eigenvalue equations
Let us consider another example.

Consider an operator: “first derivative wrt x”:
(d/dx)emx = memx;
(d/dx)sin(kx)=k cos(kx); (d/dx)cos(lx)=-l sin(lx);
In these cases; emx, is an eigenfunction of the operator (d/dx), with the

eigenvalue m, but the functions, sin(lx) and cos(kx) are not.
What about the function: cos(ky)sin(z)e-mx ? Is it an eigenfunction of

the operator (d/dx)?

A function f(x) is said to be eigenfunction of an operator if the
action of the operator on the function gives the original function
multiplied by a constant.
The constant is said to be an eigenvalue of the operator and the
equation is known as eigenvalue equation. e.g. Consider an operator:
“second derivative wrt x”:
(d2/dx2)emx = m2emx;
(d2/dx2)sin(kx)=-k2sin(kx);
(d2/dx2)cos(lx)=-l2cos(lx);
In these cases; emx, sin(kx), cos(lx), are all eigenfunctions of (d2/dx2),
with the eigenvalues m2, -k2 and -l2, respectively.
2
−nx
Homework: Show that e (where, n is a constant) is an
eigenfunction of the operator:
d2 d
+2 nx
dx 2
dx
What is the eigenvalue?

Postulate 3:
In any measurement of the observable associated with the an operator, Â, the
only values that will ever be observed are the eigenvalues, a, which satisfy
the eigenvalue equation: ÂΨ=aΨ.
When an operator operates or acts on a function, the physical interpretation of this is probing the system
to measure the corresponding observable. Initially, the system may be in some random, state. However,
when we probe to measure the observable, the probe disturbs the system and projects it to one of its
characteristic states – the eigen states of the operator. In the postulate given above, the state, Ψ, is the state
in which the system has reached after the probe is applied (and not necessarily, before its application). In
other words, the action the operator, Â has taken the system to the state, Ψ, which is the eigen state of the
operator and the eigenvalue a is obtained. At this moment, since the system has already reached in the
eigen state of Â, its further action without any time-lag would keep the state of the system unaltered and
would return the eigen value, a.

Observables and properties
Consider the (time-independent) Schrödinger equation:

H^ ψ= E ψ → Eigenvalue equation
If ψ is normalized it can be easily proven that E=∫ ψ∗ H
^ ψd τ
If ψ is not normalized, we can write E=

∫ ψ∗ H^ ψ d τ
∫ ψ∗ ψ d τ


^ ψd τ

∫ ψ∗ H^ ψ d τ
∫ ψ∗ ψ d τ
The Hamiltonian operator represents total energy of the system, so in the above
expression, the observable quantity we get is energy. If the wavefunction in the
above expression is not an eigenfunction of the Hamiltonian operator, then,
instead of exact energy, we obtain average energy.


^ ψd τ

∫ ψ∗ H^ ψ d τ
∫ ψ∗ ψ d τ
The Hamiltonian operator represents total energy of the system, so in the above
expression, the observable quantity we get is energy. If the wavefunction in the
above expression is not an eigenfunction of the Hamiltonian operator, then,
instead of exact energy, we obtain average energy.
If the Hamiltonian operator is replaced by some other operator and if the
wavefunction does not happen to be the eigenfunction of that operator, then the
average value of the corresponding observable will obtained.
⟨ A ⟩=
∫ ψ∗ A^ ψ d τ
∫ ψ∗ ψ d τ
Postulate 4:
If a system is in a state described by a wavefunction Ψ, then the average
value of an observable, Ŷ is given by
⟨Y ⟩=
∫ Y Ψdτ
Ψ
∗ ^
∫Ψ Ψd τ
∗
In this case, the state, Ψ, is a non-eigenstate of the operator, Ŷ.

Had Ψ been an eigenstate of Ŷ, then instead of the average value, one
would obtain the eigenvalue of Ŷ corresponding to the eigenstate, Ψ.

BITS Pilani
Pilani Campus

Particle in a box
• Time-dependent Schrödinger equation in 1-D

• Variable separation and time-independent SE
• Stationary states
• Well-behaved wavefunction
• Average value of observable property
• Operators, eigenvalue equations, degeneracy
• Postulates of quantum mechanics

Free particle in one
Dimension (translational motion)
Free particle → No external forces → P.E.=0
The (time independent) Schrödinger equation becomes:
2
ℏ2 d ψ( x ) d 2 ψ( x ) 2 mE
− =E ψ( x) + 2 ψ( x )=0
2 m dx 2
dx 2
ℏ
2 mE 2 d 2 ψ( x ) 2
We substitute 2
=k and it follows 2
+k ψ( x)=0
ℏ dx
What are the possible solutions? ψ( x )=sin(kx) OR ψ( x )=cos (kx )
OR ψ( x )=e ikx OR ψ( x )=e−ikx
ℏ 2 2
k p 2
h 2π h
We have, E= = . It follows, p=ℏ k= =
2m 2 m 2π λ λ
(de Broglie relation)

Particle in a (1D) box
Consider a particle in one dimension confined to a length L by infinite

potential barriers at x = 0 and x = L (infinitely deep potential well)
2
ℏ 2 d ψ( x)
− +∞ ψ( x)=E ψ( x)
2 2 m dx 2
ℏ 2 d ψ( x)
− =E ψ( x ) This equation is
2 m dx 2
well-behaved only
if the wavefunction
is zero in this
region.
V= V=
V = 0 inside box

Boundary conditions

1D-PIB wavefunctions
For x < 0 and x > L, ψ = 0 since probability of finding the particle in these
regions is zero. 2
ℏ 2 d ψ( x)
For 0≤ x ≤ L, the form of the Schrödinger equation is − =E ψ( x )
2 m dx 2

regions is zero. 2
ℏ 2 d ψ( x)
2 m dx 2
2 mE 2
Like in case of free-particle, we substitute 2
=k and get
ℏ
d 2 ψ( x) 2
What is the general solution? 2 +k ψ ( x)=0
dx

regions is zero. 2
ℏ 2 d ψ( x)
2 m dx 2
2 mE 2
=k and get
ℏ
d 2 ψ( x) 2
dx
ψ( x )= A sin (kx)+ B cos(kx)

regions is zero. 2
ℏ 2 d ψ( x)
2 m dx 2
2 mE 2
=k and get
ℏ
d 2 ψ( x) 2
dx
To solve further, we apply the boundary conditions.
Using ψ(0)=0; we get B=0; hence, ψ( x )= A sin (kx)

regions is zero. 2
ℏ 2 d ψ( x)
2 m dx 2
2 mE 2
=k and get
ℏ
d 2 ψ( x) 2
dx
Also, we have ψ(L)=0; This results two possibilities:

regions is zero. 2
ℏ 2 d ψ( x)
2 m dx 2
2 mE 2
=k and get
ℏ
d 2 ψ( x) 2
dx

Either A=0; OR, sin(kL)=0.

regions is zero. 2
ℏ 2 d ψ( x)
2 m dx 2
2 mE 2
=k and get
ℏ
d 2 ψ( x) 2
dx

Either A=0; OR, sin(kL)=0.
The solution, A=0 is discarded at it makes wavefunction identically zero.
Thus, we have sin(kL)=0.; which means, kL=nπ; n=1,2,3,….
Thus, the final solution is:
ψn ( x)= A sin ( )
nπ x
L
; n=1,2,3,... .
Quantized energy levels and wavefunctions
ψ n ( x)= A sin
L( )
nπ x
; n=1,2,3 ,…
The subscript n in the wavefunction is to indicate that the wavefunction depends

on the quantum number, n.

ψ n ( x)= A sin
L( )
nπ x
; n=1,2,3 ,…

Why did we discard n=0?
What about n=-1,-2,-3,….. ? Are they allowed? Which states do they represent?
(Find it out)

ψ n ( x)= A sin
L( )
nπ x
; n=1,2,3 ,…

(Find it out)
Homework: Normalize the wavefunction to show that constant, A=

√ 2
L
.

ψ n ( x)= A sin
L( )
nπ x
; n=1,2,3 ,…

(Find it out)
Homework: Normalize the wavefunction to show that constant, A=
The normalized wavefunctions are thus, given by

√ 2
L
.
2
ψn ( x)=
L
sin
√nπx
L( )
Energy of the system is quantized.
; n=1,2,3 ,…
ℏ 2 k 2 h2 k 2 n2 h2
E n= = 2 = ; n=1,2,3 ,…
2 m 8 π m 8 mL 2


1D-PIB
Homework: Plot qualitatively, the probability densities of the 1D-PIB

wavefunctions

Characteristics of 1D-PIB wavefunctions
Wavelength in a given state equals to 2L/n.
The number of nodes in the wavefunction equals to n-1.

The ground state wavefunction does not have nodes.
Energy increases with increase in the number of nodes. (Why?)
The wavefunctions are all symmetric or antisymmetric about the midpoint of the
box.
What will be the form of the function if the origin is shifted to the midpoint of
the box?
Non-zero energy for the ground state: E1 = h2/8mL2,
Note the dependence of the energy on m and L. As they increase, the separation
between the energy levels decreases.
As the quantum number, n tends to infinity, the probability distribution becomes

uniform over the entire length of the box.
PIB – 2D
2D or rectangular box: [V(x,y)=0 for 0 ≤x≤a ; 0 ≤y≤b and V(x,y)=∞ otherwise]
Schrödinger equation for particle in a 2D box:
( )
2 2
ℏ2 ∂ ψ ∂ ψ
− + =E ψ
2m ∂x ∂ y2 2
The motions along the two directions being independent of each other, the
wavefunction must be expressible as ψ( x , y )=ψ x ( x) ψ y ( y)
Let E = Ex + Ey. Then, one can solve to get:
−
ℏ2
2m (
ψy
d2 ψx
dx 2
+ψx
d2 ψ y
dy 2 )
=( E x +E y ) ψx ψ y
( )
2 2
ℏ 2
1 d ψ x 1 d ψy
− ψ + ψ =( E x + E y )
2m x d x 2
y d y
2
Rearranging, we have:
2 2
ℏ 2 1 d ψx ℏ2 1 d ψ y
− −E x = +E y
2 m ψ x d x2 2 m ψ y d y2

PIB – 2D
2D or rectangular box: [V(x,y)=0 for 0 ≤x≤a ; 0 ≤y≤b and V(x,y)=∞ otherwise]
We have obtained: ℏ 2 1 d 2 ψx 2
ℏ 1 d 2
ψy
− ψ −E x = ψ +E y
2m x d x 2
2m y d y 2
The LHS is a function of x alone and RHS is a function of y alone, and x and y are
independent variables. Therefore, each side would be equal to a constant. Since Ex
and Ey are unknown constants, their values may be tuned such that each side in the
above equation equals
2
to zero, and we have:
ℏ 1 d ψx
2
d 2 ψ x 2 mE x
− −E x =0 ⇒ + 2 ψ x =0 ;0≤x≤a
2 m ψ x d x2 dx 2
ℏ
2
ℏ2 1 d ψ y d 2 ψ y 2 mE y
+ E y =0 ⇒ + 2 ψ y =0 ; 0≤ y≤b
2 m ψ y d y2 dy 2
ℏ
Thus, we obtain two 1D equations which can be solved by applying the boundary
conditions to get:
( ) (
nx π x
)
ny π y
(
n2x n2y
)
2
2 h
ψn , n ( x , y)=ψx , n ( x) ψ y , n ( y )= sin sin En ,n = +
x y x y
√ ab a b x y
8 m a2 b2
n x =1,2,3 ,…; n y =1,2,3 ,…
PIB – 3D
3D box: [V(x,y,z)=0 for 0 ≤x≤a ; 0 ≤y≤b;
≤y≤b 0 ≤z≤c and V(x,y,z)=∞ otherwise]
The logic can be extended to 3D box or even multidimensional case.
( )
2 2
For 3D, the kinetic energy operator is given by − ℏ ∂2
∂ 2
∂ 2
ℏ 2
+ + ≡− ∇
2 m ∂ x2 ∂ y2 ∂ z 2 2m
The normalized wavefunction and energy are:
ψn , n
x y z
√
, n ( x , y , z)=
8
abc (
sin
a ) (
nx π x
sin
b ) ( )
ny π y
sin
nx =1,2,3 ,…; n y =1,2,3 ,…; n z =1,2,3 ,…
nz π z
c En ,n
x y ,n
z
=
h2
n
(
2
x
+
n 2
y
8 m a2 b2 c 2
+
n 2
z
)
Special cases:
Square box (2D box with both the sides equal)
Cubic box (3D box with all the sides equal)
Cuboid box (3D box with two sides equal)
Energetic degeneracy – two or more energy levels having same energy
Homework – For Square and cubic boxes, find the energies of first ten levels and
the degeneracy of each level.
BITS Pilani
Pilani Campus

Harmonic oscillator, Particle on ring and Rigid
rotor
• Particle in 1D box
●
Boundary conditions
●
Salient features of the wavefunctions and energy levels
• Particle in 2D and 3D boxes

PIB wavefunctions (revision)

Characteristics of PIB wavefunctions
(revision)
Wavelength in a given state equals to 2L/n.
The number of nodes in the wavefunction equals to n-1.

The ground state wavefunction does not have nodes.
Energy increases with increase in the number of nodes. (Why?)
The wavefunctions are alternately symmetric and antisymmetric about the

midpoint of the box.
2 nπx
√
ψ n ( x)=
L
sin( )L
; n=1,2,3 ,…
Non-zero energy for the ground state: E1 = h2/8mL2,
Note the dependence of the energy on m and L. As they increase, the separation
between the energy levels decreases.
As the quantum number, n tends to infinity, the probability distribution becomes

uniform over the entire length of the box.
PIB in two and three dimensions
(revision)
2D box: [V(x,y)=0 for 0 ≤x≤a ; 0 ≤y≤b and V(x,y)=∞ otherwise]

2 2
2 nx π x ny π y h2 n x n y
ψn , n x y
( x , y)=ψx , n ( x) ψ y , n ( y )=
x y
√ ab(sin
a ) (sin
b ) En ,n =x y
+
8 m a2 b2 ( )
n x =1,2,3 ,…; n y =1,2,3 ,…
3D box: [V(x,y,z)=0 for 0 ≤x≤a ; 0 ≤y≤b;

≤y≤b 0 ≤z≤c and V(x,y,z)=∞ otherwise]
ℏ 2 ∂2 2 2
ℏ 2
For 3D, the kinetic energy operator is given by − + ∂ + ∂ ≡−
2 m ∂ x2 ∂ y2 ∂ z 2 2m
∇
(2
)
8 nx π x ny π y nz π z 2 2 2
h2 n x n y n z
ψn , n
x y , n ( x , y , z)=
z
√
abc
sin
a (sin ) (
b
sin
nx =1,2,3 ,…; n y =1,2,3 ,…; n z =1,2,3 ,…
) ( )
c En ,n
x y ,n =
z (
+ +
8 m a2 b2 c 2 )
1D simple harmonic motion
Hooke’s law: Restoring force = -kx ( k is force constant, x is the displacement

from equilibrium)
Potential energy V(x) = ½ kx2
1D Classical harmonic oscillator –
general features
• Total energy of a classical harmonic oscillator in a given state

remains constant.
• The kinetic energy is maximum at the mean position and zero at the
turning points
• The potential energy is zero at the mean position and maximum at
the turning points
• The oscillator can be excited to a state of any arbitrary value of the
total energy

1D Quantum harmonic oscillator
Schrödinger equation for 1D harmonic oscillator is given by:

2
ℏ 2 d ψ( x) 1 2
− + kx ψ( x)=E ψ ( x) (Eq 1)
2 m dx 2 2
Boundary conditions? ψ(∞)=0=ψ(−∞)

1D Quantum harmonic oscillator
Schrödinger equation for 1D harmonic oscillator is given by:

2
ℏ 2 d ψ( x) 1 2
− + kx ψ( x)=E ψ ( x) (Eq 1)
2 m dx 2 2
Boundary conditions? ψ(∞)=0=ψ(−∞)

d 2 ψ( x) (2 mE−mkx 2 ) (Eq 2)
We rearrange Eq 1 to get: 2
+ 2
ψ( x)=0
dx ℏ
Now, we make substitutions: k/m=ω2; λ=2E/(ħω);

λ=2E/(ħω) α=mω/ħ;
α=mω/ħ y=α½x ; solve and
simply to get
d 2 ψ( y) 2
(Eq 3)
2
+(λ− y ) ψ( y )=0
dy

1D harmonic oscillator
d 2 ψ( y) 2
(Eq 3)
2
+(λ− y ) ψ( y )=0
dy
The solution of this equation is a bit involved and beyond the scope of this course.
Therefore, we will not solve it here. The solutions to the above equation have the
form:
− y2 / 2
ψv ( y)=N v H v ( y )e ; v=0,1,2 ,…
where, v is vibrational quantum number, Hv(y)(y is Hermite polynomial in y of

degree v, Nv is normalization constant for the wavefunction of the vth state.
The energy levels are non-degenerate and are given by:
1
E v =(v + )h υ; v=0,1,2 ,…; where , υ is fundamental vibrational frequency .
2
1 k
υ=
2π m√
1D harmonic oscillator
Hermite polynomials can be easily obtained using the following formula:

v − y2
d (e )
v y
2
H v ( y )=(−1) e v
; v=0,1,2 ,…
dy
H 0 ( y )=1
H 1 ( y)=2 y
H 2 ( y)=4 y 2 −2
H 3 ( y )=8 y 3 −12 y
H 4 ( y)=16 y 4 −48 y 2 +12
H 5 ( y)=32 y 5 −160 y 3 +120 y
ψ v ( y)=N v H v ( y )e
− y2 / 2 1
E v =(v + )h υ
2
1D HO: Wavefunctions and probability
distribution

1D HO: Wavefunctions and probability
distribution
v=3
v=3
v=2
v=2
v=1
v=1
v=0 v=0
Ψ (not to scale)
Ψ*Ψ
1D harmonic oscillator: characteristic
features
●
The wavefunctions are alternately even and odd functions corresponding
to the even and odd values of v (vibrational quantum number).
●
Number of nodes = v, no nodes for the ground state
● Ev=(v+½)hυ; Zero point energy E0= ½ hυ
●
For ground state, probability density is maximum at mean position. As v
increases, the probability density max gradually shifts towards the
turning points – classical limit obtained as v→∞

Particle on a ring (2D revolution)
Particle constrained to move on a ring of radius r. Take the potential

energy to be zero as long as particle on the ring, infinite otherwise
V(r=r0)=0; V(r≠r0)=∞.
Particle on a ring
Angular momentum: |⃗J|=|⃗r ×⃗p|= I ω
I =μ r 2 (Moment of intertia of the particle of mass μ moving in an orbit of radius r)
Consider the rotation in a plane orbit, say, in xy-plane, and centered at origin.
The angular momentum vector would lie along the z-axis.
In polar coordinates, the operator form for z-component of the angular

momentum is given by
ℏ d
J^ z = ; with x=r cos ϕ ; y=r sin ϕ
i dϕ
J 2z
The kinetic energy corresponding to the rotational motion is
2I
J^ 2z ℏ 2
d 2
The rotational kinetic energy operator would, thus, be =−
2I 2 I d ϕ2
Particle on a ring
We have V(r)=0 at r=r0 and infinite otherwise.
Thus, for the orbit of fixed radius, r=r0, the Schrödinger equation takes the form:
2
ℏ 2 d Φ (ϕ)
− = E Φ(ϕ)
2 I d ϕ2
The wavefunction, Φ (ϕ) for rotation about the z-axis is a pure function of the
azimuthal angle, ϕ .
The wavefunction should be single-valued and hence, its values must repeat
after each rotation, which results in the periodic boundary condition (also
referred to as cyclic boundary condition):
Φ (2 π+ϕ)=Φ (ϕ)

Particle on a ring: Boundary condition
Cyclic boundary condition (single valued):

λ = 2πr0/n; n = 0, 1, 2, 3….

Particle on a ring
ℏ 2
d 2 Φ (ϕ) d 2 Φ (ϕ) 2 IE
We have − = E Φ(ϕ) + 2 Φ (ϕ)=0
2 I d ϕ2 dϕ
2
ℏ
2
2 IE 2 d Φ (ϕ) 2
We substitute 2 =m and get 2
+m Φ(ϕ)=0
ℏ dϕ
im ϕ
The general solution is of the form Φ (ϕ)= Ae
Now we apply the periodic boundary condition and solve:

Φ (2 π+ϕ)= Ae i m(2 π+ ϕ )=Φ (ϕ)= Ae im ϕ
Ae 2 π m i e im ϕ = Ae i m ϕ
e 2 π m i=1 ⇒ m=0,±1,±2,±3,…
Homework: Normalize the wavefunction to evaluate the constant, A.

Energy Levels
Energy: m2 ℏ2 m2 h2 m2 ℏ2 m2 h2
E m= = 2 = 2
= 2 2
2I 8 π I 2 μ r0 8 π μ r0

Particle on a ring: Characteristic
features
Degeneracy of energy levels: All levels except for m=0, are doubly
degenerate, i.e. there are two distinct states of the same energy. The two differ
in the sense of the rotation
Angular momentum ȷz is quantized, ȷz = mħ
No zero point energy
What is the form of the wavefunction corresponding to m=0? Discuss the

consequences (Homework)
Compare the particle on a ring with 1D-PIB. What are the similarities and the
differences?

Particle moving on the surface of a
sphere (3D Rigid Rotor)
Polar and azimuthal angles:
Boundary conditions:
Φ (2 π+ϕ)=Φ (ϕ)
Θ(π+θ)=Θ(π−θ)
Hamiltonian eigenfunctions of rigid rotor are also the

eigenfunctions of the angular momentum squared
operator and are called spherical harmonics.
Y (θ , ϕ)=Θ(θ) Φ(ϕ)

Revolution on a sphere –
(3D) rigid rotor
Particle constrained to rotate on surface of sphere of radius R
Classically, E = J2/2mR2
Schrödinger equation involves the polar angle θ and the azimuthal
angle φ as variables
On solving, and imposing the appropriate boundary conditions,
obtain the ‘spherical harmonics,’ Yl,m (θ,φ), characterized by two
l
quantum numbers l and ml.

The spherical harmonics are a product of two functions
Yl,m (θ,φ) = Θl,m (θ)Φm (φ); ml = -l, -l+1,..0,..l-1, l
l l l
Energy El = l(l + 1)ħ2/2I ← Depends on l, not on ml

Rigid Rotor – angular momentum
Quantum number l allowed to take on values 0,1,2,…

Magnitude of the orbital angular momentum is |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. Degeneracy =2l +1
The value of the z-component of the angular momentum is mlħ.
Two aspects of the quantization of angular momentum, namely, the

magnitude of the angular momentum, and the orientation of the angular
momentum vector relative to z-axis.

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

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

BITS Pilani
Pilani Campus

Hydrogenic atom: A quantum mechanical
treatment
• 1D Harmonic oscillator
• Particle on a ring
• Rigid rotor (particle on a rigid spherical surface)

Central force field
Consider a system shown in the adjacent

figure. The yellow coloured point is
suitably chosen as origin, so that the
forces acting on the red points are aligned
along their position vectors (repulsion
with origin, shown by outward arrows).
The forces acting acting on the green

points are aligned opposite to their
position vectors (attraction with origin,
shown by inward arrows).
If there are no other forces,

forces in the system,
then such a force-field is referred to as
central force field.
field
Spherical polar coordinates are best suited for studying the systems with central-
force field.
Spherical polar coordinates
r =( x 2 + y 2 +z 2 )1/ 2 z =r cos θ
−1 z x=r sin θ cos ϕ
θ=cos
( x 2 + y 2 + z2 )1/2 y=r sin θ sin ϕ
(
ϕ= 1−
y π
|y| 2 ) +tan
−1 y

Spherical polar coordinates and
Central force field
In general, the kinetic energy can be separated into a radial kinetic energy
(describing motions along the radius (in the direction of or opposite to that of the
position vectors) plus the angular kinetic energy.
Angular kinetic energy is similar to the one for the rigid rotor problem.
One can express potential energy in spherical polar coordinates, in stead Cartesian
coordiates : V(x,y,z) → V(r, θ, φ)
However, in central force field, since the forces are dependent only on the distance
from the reference point (origin), the potential energy too, is the function of the
distance from the reference point only and is direction-independent (as is the force).
V(r, θ, φ)→central force field→ V(r) - independent of θ, φ.

φ
Examples: Rigid rotor, particle inside a spherical box, hydrogen atom, etc.

Rotation on rigid spherical surface
(revision)
●
Particle constrained to rotate on surface of sphere of radius R (rigid rotor)
●
Angular kinetic energy operator: J2/2mR2
●
Schrödinger equation involves the polar angle θ and the azimuthal angle φ as
variables
●
On solving, and imposing the appropriate boundary conditions, obtain the
‘spherical harmonics,’ Yl,ml(θ,φ),
(θ,φ) characterized by two quantum numbers l and ml.
Yl,ml(θ,φ) = Θl,ml(θ)Φml(φ);
(φ) ml = -l, -l+1,..0,..l-1, l;
l for given l, (l= 0,1,2,3,.…)
●
The orbital angular momentum quantum number l can take on the values
0,1,2,3,... (magnitude of angular momentum quantum quantized: Allowed values
are [l(l+1)]1/2ħ )
●
Orientation of the angular momentum vector also quantized (space quantization),
such that any spatial component, say z-component of the angular momentum, can
only take one of the values, mlħ,

Operator forms in spherical polar
coordinates
ℏ2 ∂ 2 ∂
K.E. Operator for radial motion: −
2μ r ∂ r
2
r(∂r )
K.E. Operator for angular motion: L2/2I
This can be fully expressed as:
[ ]
This term arises
ℏ2 1 ∂ 1 ∂2
−
2μ r sin θ
2 ∂ θ (
sin θ
∂
∂
θ
+ 2 )
sin θ ∂ ϕ
2
from the square of
the z-component of
angular momentum
2
Potential energy operator: V (r )=− Ze
4 π ε0 r
Schrödinger equation for hydrogenic
atom
Potential energy is only due to the coulombic attraction between the electron
and the nucleus
Spherical polar coordinate system is the most suitable for solving the
Schrödinger equation for hydrogenic atom:
[ ]
2
ℏ 1 ∂ 2 ∂ψ 1 ∂ ∂ψ 1 ∂2 ψ Ze 2
−
2μ r ∂ r
2
r ( + 2 )
∂ r r sin θ ∂θ
sin θ (+ 2 2 )
∂θ r sin θ ∂ ϕ2
−
4 π ϵ0 r
ψ =E ψ
KE acting on ψ PE acting on ψ
It can be proven that the quantity in the square bracket is ∇ 2 ψ

2 ∂ 2 ψ ∂ 2 ψ ∂2 ψ
∇ ψ= 2 + 2 + 2
∂x ∂y ∂z
Hydrogenic atom wavefunctions
The wavefunctions for the hydrogenic atom, in spherical polar coordinates,

may be shown to factor as
ψ(r, θ, φ) = R(r) Θ(θ) Φ(φ) = R(r) Y(θ,φ)
Further, the requirement that the wavefunction be well-behaved, (ie., single

valued, continuous,..) leads to the result that the functions are labeled by
three quantum numbers n, l, and ml ie.,
ψn,l,m (r,θ,φ) = Rn,l(r)Θl,m (θ)Φm (φ) = Rn,l(r)Yl,m (θ, φ)

l l l l
where Rn,l(r) is the radial part of ψ (radial function), and Yl,m (θ,φ) is its
l
angular part – the spherical harmonic.
Hydrogenic atom wavefunctions
Definition: Orbital is a one-electron function.

Atomic orbital is a one-electron function for an atom.
Molecular orbital is a one-electron function for a molecule* (will be
introduced in the context of molecular orbital theory, in a later module).
We see that, the wavefunctions of hydrogenic atom are atomic orbitals. Atomic
orbitals of hydrogenic atom are also referred to as hydrogenic orbitals.
Hydrogenic orbitals that are characterized by three quantum numbers* n, l,

and ml
Why three quantum numbers ?
The maximum number of physical quantities that can simultaneously be precisely
specified is three, namely, the energy, the magnitude of the angular momentum,
and one of its spatial components. The corresponding quantum numbers arise
when the conditions to be fulfilled by the wavefunction are imposed in the three
dimensions
Energy levels
Energy – Depends only on principle quantum number, n.

Obtained as Hamiltonian eigenvalues: H^ ψn ,l , m (r ,θ, ϕ)=E n ψ n ,l ,m (r ,θ ,ϕ)
l l
μ e4 Z 2
E n =− 2 2 2 2
; n=1,2,3 ,…
32 π ε 0 ℏ n
Note that energy doesn't depend on l and ml.
Energy expression coincides with the Bohr model result.
The principle quantum number, n, imposes bound on the azimuthal
quantum number, l, (l=0,1,2,...n–1), which in turn imposes
restriction on the orbital magnetic quantum number, ml,
(ml= -l, -l+1, …, 0, …, l–1, l).
The energy of a hydrogenic wavefunction depends only on the
principle quantum number, and is independent of the azimuthal and
the orbital magnetic quantum numbers.
Angular momentum – magnitude
Magnitude of Angular momentum – orbital angular momentum

quantum number (or azimuthal quantum number), l.
Hydrogenic orbitals are also eigenfunctions of L2 operator:
L2ψn,l,m = l(l + 1)ħ2 ψn,l,m

l l
Thus, the magnitude of orbital angular momentum is
|L| = [l(l + 1)]1/2ħ; l = 0,1,2,...., n–1;

n–1 for given n.
For given l, (in a given shell, characterized by n), the orbitals are
(2l+1)-fold
(2l+1) degenerate wrt L2.
Angular momentum – orientation
Orientation of L wrt +ve z-direction – (orbital) magnetic quantum

number ml.
The orbitals can be chosen* to be simultaneously, the eigenfunctions
of Lz operator: Lz ψn,l,m = mlħψn,l,m
l l
The angular momentum vector is oriented such that the eigenvalues:

Lz = mlħ ; ml = -l,-l+1,...,0,...,l-1,l; for given l.
Degeneracy: The orbitals are non-degenerate wrt Lz.
(Oribitals are characterized by unique combination of (n,l,ml)).
*more, later.

Shells, subshells and orbitals
What values can the quantum numbers take ?

n = 1, 2, 3,…..
Shell is determined by n (characterized by energy)
l = 0, 1, 2,.., n-1,
n-1 for given value of n
For a given shell (that is, for a given n), there are n subshells. Each
subshell is characterized by the radial wavefunction, Rn,l(r); (r) l
=0,1,2,3,4,5,... corresponds to s, p, d, f, g, h,.... subshells of a given
shell. Maximum value of l is n–1.
n–1
For a given subshell (that is, for a given {n,l}),
{n,l} there are 2l+1 orbitals
corresponding to ml=-l, -l+1, …, 0, …, l–1, l.l
How many orbitals for a given n? → n2

Example: l = 1, ml = 1,0,-1

Example: l = 2, ml = 2,1,0,-1,-2

Hydrogenic orbitals-characteristics
The general form is ψn,l,m (r,θ,φ) = Rn,l(r)Yl,m (θ, φ)

l l
Number of radial nodes is determined from the Radial function and equals
to the degree of polynomial in r.
Azimuthal quantum number equals to Principle quantum number

number of angular nodes
Yl,m (θ, φ) are spherical harmonics: Polynomial of degree, “l–|ml|” in cosθ times
l
(sinθ)m multiplied by Φm (φ)
l
The radial function determines the sub-shell.

Spherical Harmonics (FYI)
The spherical harmonics, Yl,m (θ,φ),

θ,φ) provide the angular parts of the hydrogenic
l
orbitals, that is, hydrogenic wavefunctions. These are expressible as product of the
polar (θ-dependent) and the azimuthal (φ-dependent) parts.
Y l, m (θ, ϕ)=Θl, m (θ) Φ m ( ϕ)
l l l
Θ0,0 (θ)=P0,0
Θ1,0 (θ)= P1,0 cos θ
Θ1,±1 (θ)= P1,±1 sin θ
±i m l ϕ
2 Φ±m (ϕ)=e
Θ2,0 (θ)=P 2,0 3cos θ−1 l
'
Θ2 ,±1 (θ)=P2 ,±1 sin 2θ≡P 2,±1 sin θ cosθ
2
Θ2 ,±2 (θ)=P 2,±2 sin θ
3
Θ3,0 (θ)=P3,0 5 cos θ−3cos θ
2
Θ3, ±1 (θ)= P3,±1 sin θ(5cos θ−1)
2
Θ3, ±2 (θ)=P3 ,±2 sin θ cosθ
(The Pl,m ’s are the normalization constants)
Θ3, ±3 (θ)=P3, ±3 sin3 θ l

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Hydrogenic wavefunctions –
characterization, analysis, spectroscopy
• Central force field

• Hamiltonian operator in spherical polar coordinates
• Radial functions and spherical harmonics
• The three quantum numbers
• Orbitals, atomic orbitals, hydrogenic orbitals

Spherical polar coordinates (revision)
r =( x 2 + y 2 +z 2 )1/ 2 z =r cos θ
−1 z x=r sin θ cos ϕ
θ=cos
( x 2 + y 2 + z2 )1/2 y=r sin θ sin ϕ
y π −1 y
(
ϕ= 1−
|y| 2 ) +tan
x

Spherical Harmonics (FYI)
The spherical harmonics, Yl,m (θ,φ),

θ,φ) provide the angular parts of the hydrogenic
l
orbitals, that is, hydrogenic wavefunctions. These are expressible as product of the
polar (θ-dependent) and the azimuthal (φ-dependent) parts.
Y l, m (θ, ϕ)=Θl, m (θ) Φ m ( ϕ)
l l l
Θ0,0 (θ)=P0,0
Θ1,0 (θ)= P1,0 cos θ
Θ1,±1 (θ)= P1,±1 sin θ
±i m l ϕ
2 Φ±m (ϕ)=e
Θ2,0 (θ)=P 2,0 3cos θ−1 l
'
Θ2 ,±1 (θ)=P2 ,±1 sin 2θ≡P 2,±1 sin θ cosθ
2
Θ2 ,±2 (θ)=P 2,±2 sin θ
3
Θ3,0 (θ)=P3,0 5 cos θ−3cos θ
2
Θ3, ±1 (θ)= P3,±1 sin θ(5cos θ−1)
2
Θ3, ±2 (θ)=P3 ,±2 sin θ cosθ
(The Pl,m ’s are the normalization constants)
Θ3, ±3 (θ)=P3, ±3 sin3 θ l

Radial functions
The general form of orbitals is ψn,l,m (r,θ,φ) = Rn,l(r)Yl,m (θ, φ)

l l
Number of radial nodes is determined from the Radial function and equals
to the degree of polynomial in r.
Azimuthal quantum number equals to Principle quantum number

number of angular nodes
Yl,ml(θ, φ) are spherical harmonics: Polynomial of degree, “l–|ml|” in cosθ
times (sinθ)m multiplied by Φml(φ)
l
The radial function determines the sub-shell.

Orbitals with zero orbital angular
momentum
The wavefunctions corresponding to l=0 are called s-type orbitals. They are
independent of of θ and φ. In other words, the angular wavefunction is
constant.
For example,
Note: In all the orbital expressions, the normalization constant, M is distinct.

Orbitals with angular momentum
vector lying in xy-plane
These orbitals are characterized by ml=0 by virtue of zero z-component of the
angular momentum. These orbitals are independent of the azimuthal angle, φ.
Excluding the s-orbitals (i.e., l=0, since, already discussed), these are
characterized by global maxima of probability density along +z and -z
directions and are symmetric with respect to rotation about the z-axis.
For example,
Note: In all the orbital expressions, M is normalization constant and is

different for different orbitals.
Orbitals with angular momentum
vector lying in xy-plane
These orbitals are characterized by ml=0 by virtue of zero z-component of the
angular momentum. These orbitals are independent of the azimuthal angle, φ.
Excluding the s-orbitals (i.e., l=0, since, already discussed), these are
characterized by global maxima of probability density along +z and -z
directions and are symmetric with respect to rotation about the z-axis.
For example,

Orbitals with non-zero z-component
of orbital angular momentum
These orbitals are characterized by l>0, |ml|>0. If one probes to measure the
exact value of z-component of the angular momentum in addition to its
magnitude, the orbitals are complex with Φm (φ) = eimlφ
l
For example,

Orientation-instructive orbitals versus
Lz-eigenstates
Unlike in other orbtitals, when considering orbitals with l>0, ml≠0, which are the Lz-
eigenstates, the regions of probability density maxima are not deternminate.
However, one can take appropriate linear combinations of the pair of orbitals
corresponding to (n, l, ±ml), to get a pair of orbitals, for which the probability density
maxima can be easily located, at the cost of the z-component of the angular
momentum – the sign of the z-component of the angular momentum becomes
uncertain.
For example,

Lz-eigenstates
uncertain.
For example,

Lz-eigenstates
uncertain.
For example,

Radial functions (R(r))
R(r)
Homework:
Using the expressions for
R(r) provided in the
“additional resources”
section on nalanda-aws,
plot Rn,l(r) versus r for 1s,
2s, 2p, 3s, 3p, 3d and obtain
the values of r
corresponding to the radial
nodes in the orbitals.

Hydrogenic orbital pictures
(isodensity surfaces)
1s 2s 3s
(These Pictures have been generated using Q-Chem 5.3 and IQmol)
2 pz 2 px 2 py
3 pz 3 px 3 py
3 d xz 3 dx −y
2 2
3 d z ≡3 d 3 z −r
2 2 2
3 d yz 3 d xy
1s wavefunction and probability
density

Radial probability distribution
Radial probability distribution function: Probability that electron will be found

between r and r+dr from the nucleus, regardless of the angle/direction. The
volume element is dxdydz = r2drsinθdθdφ
The s-type orbitals are independent of θ and φ. Integrating over the angular part
leaves a factor of 4π.
Thus, for s-type orbitals, P(r)dr = 4πr2R2dr
More generally P(r) = r2R2(r);

(r) (for orbitals with l>0)
where R(r) is the radial wavefunction

Radial probability distribution for 1s
state
Most probable distance from the nucleus = a0

How to obtain this?
Set dP(r)/dr=0 and
calculate r.
P(r) = r2R2(r)
For the 1s orbital, P(r) = (4/a03) 4πr2 e-2r/a0

Hydrogenic orbitals are mutually
orthonormal
Orthogonal functions: The functions, ψi and ψ j are said to be orthogonal, if they
satisfy the following:
∫ ψ∗i ψ j d τ=0 ; for i≠ j
If additionally, both ψi and ψ j are normalized then they are said to be orthonormal
(orthogonal + normalized) and we have
∗
∫ ψi ψ j d τ=δij
Where, the δij is the Kronecker delta function which satisfies
δii =1=δ jj ; δij=0 ∀ i≠ j
Orthogonality of hydrogenic orbitals can be easily tested.
Homework: Test the orthogonality between
(I) PIB wavefunctions (any two states)
(II) Harmonic oscillator wavefunctions (any two states)
(III) Particle-on-a-ring wavefunctions (any two states – mind the complex conjugates)
Electron spin
Intrinsic angular momentum, and associated magnetic moment,

characteristic of electron, a property like its mass, charge etc.
First indicated by spectroscopic features, eg., the doublet Na D
‘line’
Confirmed by the Stern Gerlach experiment. A beam of atoms
passed through a magnetic field strongly inhomogeneous in, say, the
z direction. Two beams emerge – the magnetic moment can take
only two orientations with respect to the chosen axis.

Stern Gerlach experiment
Classically
expected result
z-axis
Experimental Result
(Ag atoms)
Electron spin
Electron spin described by spin angular momentum quantum number: s = ½

Magnitude of spin angular momentum:
[½(½+1)]½ħ = (3/4)½ħ
Orientation of spin angular momentum

is quantized according to the quantum
number ms:
(In general, ms = -s,-s+1,...,s-1,s)
Consequently, for electron z-component of spin angular moment is ħ/2 or -ħ/2,

corresponding to ms = 1/2 (α) or -1/2 (β), respectively.

Emission spectra of hydrogenic atoms
Selection rules:
The allowed electronic transitions in a hydrogenic atom are those in which
the orbital angular momentum quantum number of the atom changes by
one unit. The orbital magnetic quantum number may change at the most by
one unit. The spin magnetic quantum number remains unchanged during
the transition.
Δl=±1, Δml=0,±1, Δms=0
Origin? Conservation of angular momentum:
Photon has spin angular momentum = 21/2ħ corresponding to sphoton=1

Grotrian diagram
Δl=±1, Δml=0,±1
Δms=0
(Obviously, Δn≠0)
Δn≠0

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Many electron atoms
• Hydrogenic orbitals
• Radial functions and radial nodes
• Isodensity surfaces, angular nodes
• Probability density and probability distribution
• Electron-spin and selection rules for atomic spectra of
hydrogenic atoms

Emission spectra of hydrogenic atoms
(revision)
Selection rules:
The allowed electronic transitions in a hydrogenic atom are those in which
the orbital angular momentum quantum number of the atom changes by
one unit. The orbital magnetic quantum number may change at the most by
one unit. The spin magnetic quantum number remains unchanged during
the transition.
Δl=±1, Δml=0,±1, Δms=0
Origin? Conservation of angular momentum:
Photon has spin angular momentum = 21/2ħ corresponding to sproton=1

Grotrian diagram (revision)
Δl=±1, Δml=0,±1
Δms=0
(Obviously, Δn≠0)
Δn≠0

Electron spin (revision)
Electron spin described by spin angular momentum quantum number: s = ½

Magnitude of spin angular momentum:
[½(½+1)]½ħ = (3/4)½ħ
Orientation of spin angular momentum

is quantized according to the quantum
number ms:
(In general, ms = -s,-s+1,...,s-1,s)
Consequently, for electron z-component of spin angular moment is ħ/2 or -ħ/2,

corresponding to ms = 1/2 (α) or -1/2 (β), respectively.

Many electron atoms
Hamiltonian:
2 2 2 2 2
ℏ 2 ℏ 2 2 Ze Ze e
− ∇N− ( ∇ 1 + ∇ 2 +…)− − −…+ +…
2 mN 2 me 4 π ϵ 0 r 1 4 π ϵ0 r 2 4 π ϵ0 r 12
(K.E)N (K.E.)e VNe Vee
The exact solution of Schrödinger equation for atoms with two or more electrons
is impossible. (Vee is the bottleneck – due fast motion of electrons)
However, approximate wavefunctions and energies can be computed with a
tunable accurately.
Consider Vee in approximate way – make separable Hamiltonian

Pauli principle
When the labels of any two identical fermions (½ integer spin) are exchanged,
the total wavefunction (including spin) changes sign. (ANTI-SYMMETRIC
under exchange)
For Fermions:
ψ( x̄ 1 … x̄ i −1 , x̄ i , x̄ i +1 … x̄ j −1 , x̄ j , x̄ j +1 … x̄ n )=−ψ( x̄ 1 … x̄ i −1 , x̄ j , x̄ i+1 … x̄ j−1 , x̄ i , x̄ j +1 … x̄ n )
When the labels of any two identical bosons (integer spin) are exchanged, the
total wavefunction (including spin) remains the same. (SYMMETRIC under
exchange).
For Bosons:
ψ( x̄ 1 … x̄ i −1 , x̄ i , x̄ i +1 … x̄ j −1 , x̄ j , x̄ j +1 … x̄ n )=ψ( x̄ 1 … x̄ i−1 , x̄ j , x̄ i + 1 … x̄ j −1 , x̄ i , x̄ j +1 … x̄ n )
x̄≡{⃗r , spin}
Many electron atoms: Orbital
approximation
Wavefunction for many-electron atom: Ψ(1,2,…)

Pauli principle says that the wavefunction should be anti-symmetric with
respect to interchange of space-spin coordinates of any two electrons.
Orbital approximation: Approximate the wavefunction as a product of one
electron functions or orbitals.
Ψ(1,2,…) = ψ1(1)ψ2(2)….. {multiplied by spin parts}*
How correspondingly are we approximating the Hamiltonian? Each orbital
may be thought of as being hydrogen-like with an effective nuclear charge
(effect of average e-e repulsion included).
*anti-symmetry to be ensured
α(ω): for m s =1/2

Spin functions: ∫ α(ω)∗ α(ω) d ω=1=∫ β(ω)∗ β(ω) d ω
β(ω): for m s=−1/ 2 ∫ α(ω)∗ β(ω) d ω=0=∫ β(ω)∗ α(ω) d ω
Spin-orbitals
Spin-orbital is an orbital multiplied by the electron-spin function.

e.g. Hydrogenic spin-orbitals: State of a hydrogenic atom is completely described by
a hydrogenic spin-orbitals (characterized by four quantum numbers: n, l, ml and ms).
1s_α → n=1, l=0, ml=0, ms=1/2
1s_β → n=1, l=0, ml=0, ms=-1/2
2pz_α → n=2, l=1, ml=0, ms=1/2
2p1_β → n=2, l=1, ml=1, ms=-1/2; and so on.
Hydrogenic spin-orbitals describe the electronic state of the hydrogenic atom
completely.
For a many electron atom, with the wavefunction described using orbital
approximation, no two electrons can have same spin-orbital according to Pauli
principle.

Form of many electron wavefunctions:
two-electron case
Two electrons in same orbital (spatial function) Φ:
ψ( x̄ 1 , x̄ 2 )=ϕ(⃗r 1 )ϕ(⃗r 2 )×{spin− part }, that is, ψ(1,2)=ϕ(1) ϕ(2)×{spin− part }
Pauli principle: ψ( x̄ 2 , x̄ 1 )=−ψ( x̄ 1 , x̄ 2 ) (MUST BE FOLLOWED!)

How the spin part could be?
α(ω1 )α(ω2 )[≡α(1)α(2)]
OR
β(ω1 )β(ω2 )[≡β(1)β(2)]
(same spin) ?
α(ω1 )β(ω2 )[≡α(1)β(2)]

OR
β(ω1 )α(ω2 )[≡β(1)α (2)]
(opposite spin) ?
Form of two-electron wavefunction;
paired electrons
What will be the form of the wavefunction?

paired electrons
ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 )α(1)α (2) ?

paired electrons
ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 )α(1)α (2) ?
ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 ) β(1) β(2) ?

paired electrons
ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 )α(1)α (2) ?
ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 ) β(1) β(2) ?

1
ψ( x̄ 1 , x̄ 2 )= ϕ( ⃗r 1 )ϕ( ⃗r 2 ){α (1)β(2)+β(1)α(2)} ?
√2

paired electrons
ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 )α(1)α (2) ?
ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 ) β(1) β(2) ?

1
ψ( x̄ 1 , x̄ 2 )= ϕ( ⃗r 1 )ϕ( ⃗r 2 ){α (1)β(2)+β(1)α(2)} ?
√2
1
ψ( x̄ 1 , x̄ 2 )= ϕ( ⃗r 1 )ϕ( ⃗r 2 ){α (1)β(2)−β(1) α(2)} ?
√2

paired electrons
ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 )α(1)α (2) ?
ψ( x̄ 1 , x̄ 2 )=ϕ( ⃗r 1 )ϕ ( ⃗r 2 ) β(1) β(2) ?

1
ψ( x̄ 1 , x̄ 2 )= ϕ( ⃗r 1 )ϕ( ⃗r 2 ){α (1)β(2)+β(1)α(2)} ?
√2
1
ψ( x̄ 1 , x̄ 2 )= ϕ( ⃗r 1 )ϕ( ⃗r 2 ){α (1)β(2)−β(1) α(2)} ?
√2
The only form that leads to anti-symmetric wavefunction with respect to

interchange of the coordinates of the electrons is
1
ψ( x̄ 1 , x̄ 2 )= ϕ( ⃗r 1 )ϕ( ⃗r 2 ){α(1)β(2)−β (1)α(2)}
√2

Anti-symmetry in electronic states with
unpaired electrons
What will be the valid forms of the spatial part of the wavefunction?
The overall wavefunction can be anti-symmetric, if a symmetric spatial part is

multiplied to anti-symmetric spin part and vice versa.

unpaired electrons
ψ(1,2) spatial =[ ϕ i ( ⃗r 1 ) ϕ j ( ⃗r 2 )+ϕ j ( ⃗r 1 ) ϕ i ( ⃗r 2 )] (case A : spatial part symmetric )


unpaired electrons
ψ(1,2) spatial =[ϕ i ( ⃗r 1 ) ϕ j ( ⃗r 2 )−ϕ j ( ⃗r 1 ) ϕ i ( ⃗r 2 )] (case B : spatial part anti −symmetric )


unpaired electrons

1
Anti-symmetric spin part – only option is: [α (1)β(2)−β(1)α(2)]
√2

unpaired electrons

1
√2
α(1)α (2)
1
Symmetric spin part – three possibilities: [α (1)β(2)+β(1)α(2)]
√2
β(1)β(2)
unpaired electrons

1 S=0, MS=0
√2
α(1)α (2)
1
√2
β(1)β(2)
unpaired electrons

1 S=0, MS=0
√2
α(1)α (2) S=1, MS=1

1 S=1, MS=0
√2
β(1)β(2) S=1, MS=-1

unpaired electrons
Thus, the valid wavefunctions are:
1
ψs ( x̄ 1 , x̄ 2 )= N spatial , s [ϕ i ( ⃗r 1 )ϕ j ( ⃗r 2 )+ϕ j ( ⃗r 1 ) ϕi ( ⃗r 2 )][α(1)β(2)−β(1)α (2)]
√2
ψt ( x̄1 , x̄ 2 )( M S = 1)= N spatial , t [ϕi ( ⃗r 1 ) ϕ j ( ⃗r 2 )−ϕ j ( ⃗r 1 ) ϕi ( ⃗r 2 )]α(1)α (2)
1
ψt ( x̄1 , x̄ 2 )( M S = 0)= N [ϕ ( ⃗r )ϕ ( ⃗r )−ϕ j ( ⃗r 1 )ϕi ( ⃗r 2 )][α(1)β(2)+β(1) α(2)]
√ 2 spatial , t i 1 j 2
ψt ( x̄1 , x̄ 2 )( M S =−1)= N spatial ,t [ϕ i (⃗r 1 )ϕ j (⃗r 2 )−ϕ j (⃗r 1 )ϕi (⃗r 2 )]β(1)β(2)
Hamiltonian does not depend on the electron spin, and the energy would depend only on the
spatial part of the wavefunctions.
Thus, there is only one state corresponding to the antisymmetric spin arrangement and is
called singlet.
There are three states (same spatial part, same energy) corresponding to symmetric spin
arrangements and result in a triplet.
What happens to the singlet and triplet wavefunctions when the two electrons approach each
other?

BITS Pilani
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Many electron atoms
• Many-electron atoms – Hamiltonian operator

• Pauli principle and anti-symmetry
• Orbital approximation, spin-orbitals
• Wavefunctions for high-spin and low-spin states

Many electron atoms (revision)
Hamiltonian:
2 2 2 2 2
ℏ 2 ℏ 2 2 Ze Ze e
− ∇N− ( ∇ 1 + ∇ 2 +…)− − −…+ +…
2 mN 2 me 4 π ϵ 0 r 1 4 π ϵ0 r 2 4 π ϵ0 r 12
(K.E)N (K.E.)e VNe Vee
According to Pauli principle, the wavefunction of a many-electron system

must be anti-symmetric with respect to interchange of the coordinates of any
two electrons.
ψ( x̄ 1 … x̄ i −1 , x̄ i , x̄ i +1 … x̄ j −1 , x̄ j , x̄ j +1 … x̄ n )=−ψ( x̄ 1 … x̄ i −1 , x̄ j , x̄ i+1 … x̄ j−1 , x̄ i , x̄ j +1 … x̄ n )
x̄≡{⃗r , spin}

Anti-symmetry in electronic states:
(revision)
Thus, the valid wavefunctions are:

1
ψs ( x̄ 1 , x̄ 2 )= N spatial , s [ϕ i ( ⃗r 1 )ϕ j ( ⃗r 2 )+ϕ j ( ⃗r 1 ) ϕi ( ⃗r 2 )][α(1)β(2)−β(1)α (2)]
√2
ψt ( x̄1 , x̄ 2 )( M S = 1)= N spatial , t [ϕi ( ⃗r 1 ) ϕ j ( ⃗r 2 )−ϕ j ( ⃗r 1 ) ϕi ( ⃗r 2 )]α(1)α (2)
1
ψt ( x̄1 , x̄ 2 )( M S = 0)= N [ϕ ( ⃗r )ϕ ( ⃗r )−ϕ j ( ⃗r 1 )ϕi ( ⃗r 2 )][α(1)β(2)+β(1) α(2)]
√ 2 spatial , t i 1 j 2
ψt ( x̄1 , x̄ 2 )( M S =−1)= N spatial ,t [ϕ i (⃗r 1 )ϕ j (⃗r 2 )−ϕ j (⃗r 1 )ϕi (⃗r 2 )]β(1)β(2)
Hamiltonian does not depend on the electron spin, and the energy would depend only on the
spatial part of the wavefunctions. Thus, there is only one state corresponding to the anti-
symmetric spin arrangement and is called singlet. There are three states (same spatial part,
same energy) corresponding to symmetric spin arrangements and thus form a triplet.
What happens to the singlet and triplet wavefunctions when the two electrons approach each
other?
In triplet state, the wavefunction vanishes when the electrons approach each other, thereby,
effectively reducing the electron-electron repulsion. Thus, the energy of a high-spin state is
lowered as compared to the corresponding low-spin state.

Orbital approximation: He atom
The orbital approximation allows us to express the electronic structure of an atom

in terms of its configuration, the list of occupied orbitals.
For example, we ignore the inter-electronic repulsion, the ground state
wavefunction of He could be written as
( ) ( )
1/ 2 1/ 2
8 −2 r 1 / a 0 8 −2 r 2 / a0
ψ spatial (1,2)= 3
e 3
e
π a0 π a0


( ) ( )
1/ 2 1/ 2
8 −2 r 1 / a 0 8 −2 r 2 / a0
ψ spatial (1,2)= 3
e 3
e
π a0 π a0
Including the spin-part, the total wavefunction becomes:
ψ( x̄ 1 , x̄ 2 )=
( )
1 8
√ 2 π a0
3
e
−2 (r +r )/ a
[α(1)β(2)−β(1)α( 2)]
1 2 0
corresponding to the configuration 1s2, with the 1s orbital being somewhat more
compact than in H.


( ) ( )
1/ 2 1/ 2
8 −2 r 1 / a 0 8 −2 r 2 / a0
ψ spatial (1,2)= 3
e 3
e
π a0 π a0
Including the spin-part, the total wavefunction becomes:
ψ( x̄ 1 , x̄ 2 )=
( )
1 8
√ 2 π a0
3
e
−2 (r +r )/ a
[α(1)β(2)−β(1)α( 2)]
1 2 0
corresponding to the configuration 1s2, with the 1s orbital being somewhat more
compact than in H.
What about Li? (Can all 3 electrons occupy 1s orbital ?)
Orbital approximation
No two electrons can have same spin-orbital. (Pauli principle revisited)

If two electrons have same spatial orbital, then their spins must be
different (paired).
The two electrons with paired spins have zero net spin angular momentum.
(S=0,
S=0 hence, MS=0).
=0
An orbital can accommodate maximum two electrons.
This principle forms the basis of the electronic structure of atoms,

chemical periodicity, and molecular structure.
The third electron in Li must enter the n =2 shell, but the 2s or the 2p?
2p
Shielding
In a many electron atom, each electron is shielded from the nucleus by the
others, and under a fair approximation, each electron may be thought of as
experiencing an effective nuclear charge (which is less than the actual nuclear
charge).
The effective nuclear charge will be determined by electron probability

density distribution, and this is, in turn, determined by its wavefunction.
Electrons in s-type orbitals shield more effectively than the ones in p-type, d-
type,... orbitals.
Penetration
The radial probability distribution function for s-type orbitals is

greater than the p-, d-, etc type orbitals of the given shell.

Order of occupation
The penetration of an ‘s’ electron is greater as compared to a ‘p’ electron of

the same shell implies that it experiences a greater effective nuclear charge.
In turn, the effective nuclear charge experienced by the ‘p’ electron will be
greater than that for a ‘d’ electron in the same shell. In general therefore, in
the same shell of a many-electron atom, the order of energies of the
subshells is s < p < d < f.
Thus, the ground electronic configuration of Li is therefore 1s22s1, or

[He]2s1.

Order of occupation
Aufbau principle: (Building up principle) – The sub-shells usually

get filled in the sequence:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s, …
Every orbital can consider two possible spin orientations resulting in

two spin-orbitals. Thus, every orbital can accommodate two
electrons. Consequently, a sub-shell corresponding to azimuthal
quantum number, l, (for given n, obviously,) can accommodate up
to 4l+2 electrons.

Ground state electronic configuration
(under orbital approximation)
H: 1s1 F: [He]2s22p5
He: 1s2 Ne: [He]2s22p6
Li: 1s22s1 → [He]2s1 Na: [He]2s22p63s1 → [Ne]3s1
Be: 1s22s2 → [He]2s2 Al: [Ne]3s23p1
B: 1s22s22p1 → [He]2s22p1 Ar: [Ne]3s23p6
C: 1s22s22p2 → [He]2s22p2 Sc: [Ar]3d14s2
N: 1s22s22p3 → [He]2s22p3 Zr: [Kr]4d15s2
O: 1s22s22p4 → [He]2s22p4 Ce: [Xe]4f15d16s2

Electronic configuration of atoms
Question: How many states of a Carbon atom correspond to the electronic

configuration: 1s22s22p2 ?


Answer: The 1s and 2s subshells are completely filled. The two electrons
in 2p subshell can be arranged in 6C2 = 15 possible ways → 15 states.


Question: Are all these states energetically degenerate?



Answer: No. Not all of them have same energy.



Question: What are the factors affecting the energies of these states?.



Question: What are the factors affecting the energies of these states?
Answer: The spin angular momentum and orbital angular momentum of
electrons and the coupling between these two – spin-orbit interactions.

Orbital and spin angular momenta
Do they interact with one-another?

Magnetic moment from spin
Electron has spin angular momentum
Moving charges generate magnetic fields
Magnetic field generated from spin
Magnetic moment from orbital angular momentum
Electron has orbital angular momentum if l>0.
In effect a circulating current
Magnetic field generated from orbital momentum

Spin and orbital angular momenta:
Interaction energy
l HIGH ENERGY
Magnetic moments are
parallel (angular momenta
are parallel)
s
l LOW ENERGY
Magnetic moments are
s antiparallel (angular
momenta are antiparallel)
Energy depends on relative orientation of spin- and orbital- angular

momenta
Spin orbit coupling
Energy of the spin-orbit coupling is given by:

E spin−orbit ∝ [ j ( j+1)−l (l +1)−s( s+1)]
E spin−orbit = c spin−orbit [ j ( j+1)−l (l +1)−s( s+1)]

What is the origin of this formula?
Energy is proportional to the square of the angular momentum.

⃗J =L
⃗ +S
⃗
J2=⃗J⋅⃗J =( L
⃗ +S
⃗ )⋅( L
⃗ +S
⃗ )=L
⃗⋅L
⃗ +S
⃗⋅S
⃗ +2 L
⃗⋅S
⃗ =L2 +S 2 + 2 L
⃗⋅S
⃗
⃗⋅S
J 2− L 2 − S 2 = 2 L ⃗ ⇐ spin−orbit coupling
J2= j( j+1) ℏ 2 ; L2=l (l +1) ℏ 2 ; S2 =s ( s+1) ℏ 2

Spin orbit coupling

For a single electron, s= ½;
If the electron is in s-type orbital, then orbital angular momentum is zero;

thus, l=0 → j=s=½
E α {j(j+1)–l(l+1)–s(s+1)} ={½(½+1)–0 –½(½+1)}=0
No spin orbit coupling.
In other cases, spin-orbital coupling will result in change in the energy →

different energy levels obtained

Spin orbit coupling for one electron
⃗ + ⃗S
Vector addition: ⃗J = L
Case: Vectors Case: Vectors
Case: Vectors
aligned oppositely differently
aligned in same
aligned
direction
⃗ |+|⃗S |
|⃗J |=|L ⃗ |−|⃗S ||
|⃗J |=||L ⃗ |−|⃗S |≤|⃗J |≤|L
|L ⃗ |+|⃗S |
⃗S
⃗S ⃗S
⃗ ⃗
L
L
⃗
L ⃗J ⃗J
⃗J
Components of vectors add like scalars.

Spin orbit coupling in many-electron
atoms – heavy atoms
For heavy atoms, the effective nuclear charge is very large,

consequently, the magnetic moments induced in the electrons as a
result of relative motions of nuclei (corresponding to orbital and
spin motions of electrons) are very large. The orbital magnetic
moment and the spin magnetic moment of each electron strongly
couple to give the total electronic magnetic moment of the
electron corresponding to the total angular momentum of the
electron, (quantum number j).
The total angular momentum of the atom (quantum number J) is
obtained by adding the total angular momenta of all the electrons
– j-j coupling.

atoms – light atoms
For light atoms, the effective nuclear charge is relatively small. The
spin-orbit interactions are very small and to a very good
approximation, one can calculate the total orbital angular momentum
of the atom (quantum number L; vector sum of the orbital angular
momenta of all electrons) and analogously, the total spin angular
momentum (quantum number S) of the atom.
The total angular momentum of the atom (quantum number J) can be
viewed as the resultant of the total orbital and total spin contributions
– LS coupling.
In this course, we will briefly study only the LS coupling.
(Also known as RS coupling after Russell and Saunders who
introduced it)

BITS Pilani
Pilani Campus

Terms, levels, term symbols and electronic
spectra of many-electron atoms
• Wavefunctions for high-spin and low-spin states

• Shielding, penetration and Aufbau principle
• Relative motion of charges and spin-orbit interactions
• Terms, levels and term symbols

Spin orbit coupling (revision)


What is the origin of this formula?
Energy is proportional to the square of the angular momentum.

⃗J =L
⃗ +S
⃗
J2=⃗J⋅⃗J =( L
⃗ +S
⃗ )⋅( L
⃗ +S
⃗ )=L
⃗⋅L
⃗ +S
⃗⋅S
⃗ +2 L
⃗⋅S
⃗ =L2 +S 2 + 2 L
⃗⋅S
⃗
⃗⋅S
J 2− L 2 − S 2 = 2 L ⃗ ⇐ spin−orbit coupling
J2= j( j+1) ℏ 2 ; L2=l (l +1) ℏ 2 ; S2 =s ( s+1) ℏ 2

Spin orbit coupling for one electron
(revision)
⃗ + ⃗S
Vector addition: ⃗J = L
Case: Vectors Case: Vectors
Case: Vectors
aligned oppositely differently
aligned in same
aligned
direction
⃗ |+|⃗S |
|⃗J |=|L ⃗ |−|⃗S ||
|⃗J |=||L ⃗ |−|⃗S |≤|⃗J |≤|L
|L ⃗ |+|⃗S |
⃗S
⃗S ⃗S
⃗ ⃗
L
L
⃗
L ⃗J ⃗J
⃗J
Components of vectors add like scalars.

atoms – heavy atoms (revision)
For heavy atoms, the effective nuclear charge is very large,

consequently, the magnetic moments induced in the electrons as a
result of relative motions of nuclei (corresponding to orbital and
spin motions of electrons) are very large. The orbital magnetic
moment and the spin magnetic moment of each electron strongly
couple to give the total electronic magnetic moment of the
electron corresponding to the total angular momentum of the
electron, (quantum number j).
The total angular momentum of the atom (quantum number J) is
obtained by adding the total angular momenta of all the electrons
– j-j coupling.

atoms – light atoms (revision)
For light atoms, the effective nuclear charge is relatively small. The
spin-orbit interactions are very small and to a very good
approximation, one can calculate the total orbital angular momentum
of the atom (quantum number L; vector sum of the orbital angular
momenta of all electrons) and analogously, the total spin angular
momentum (quantum number S) of the atom.
The total angular momentum of the atom (quantum number J) can be
viewed as the resultant of the total orbital and total spin contributions
– LS coupling.
In this course, we will briefly study only the LS coupling.
(Also known as RS coupling after Russell and Saunders who
introduced it)

Terms and Levels (in LS coupling)
The set of electronic states of an atom corresponding to a given set

of total orbital angular momentum and total spin angular
momentum constitute a term.
Using the total orbital angular momentum quantum number (L) and
total spin angular momentum quantum number (S), the term is
represented by term symbol of the form:
2S+1
(spectroscopic symbol for L)
Spectroscopic symbols are: S,P,D,F,G,H,I... for L=0,1,2,3,4,5,6....

Terms and Levels
Upon considering the spin-orbit interactions, the term splits into

levels characterized by the total angular momentum quantum
number, J. The levels of a term are represented by subscripting the
total angular momentum quantum number (J) on the right of the
corresponding term symbol:
2S+1
(spectroscopic symbol for L)J.
J=L+S, L+S-1,....., |L-S|

Terms and levels for one-electron
atoms
For a single electron case, there L=l and S=s,

S=s and consequently,
there is only one term. For L=l=0,
L=l=0 there is only one level with
J=S=s;
J=S=s whereas, for L>0,
L>0 there are two levels.
e.g.
L=l=0 → term: 2S → level: 2S1/2
L=l=1 → term: 2P → levels: 2P3/2 and 2P1/2
L=l=2 → term: 2D → levels: 2D5/2 and 2D3/2 and so on.

Terms and levels for many-electron
atoms
Example: two electron case -

Electronic configuration 1s2: L=l1+l2=0;
=0 S=0 because the electrons
are paired. Hence, the only term is 1S with the only level, 1S0.
What about the electronic configuration 1s12s1 ?

Since the electrons are unpaired, there are four possible spin-
orientation resulting in a triplet (S=1)
S=1 and a singlet (S=0),
S=0 the terms
are 3S and 1S with levels, 3S1 and 1S0, respectively.

atoms
Terms and levels for e.c. 1s22s1? – same as for 1s1

(Term: 2S; Level: 2S1/2)
Terms and levels for e.c. 1s22s2or 1s22s22p6? – same as for 1s2
(Term: 1S; Level: 1S0)
Observation: s-subshells do not contribute to L, completely subshells
do not contribute to L and S.
Terms and levels for e.c. 1s22s12p1?
L=1, S=1,0 → Terms: 3P, 1P
Levels for 3P: 3P2, 3P1, 3P0; Levels for 1P: 1P1
atoms: Electrons in different sub-
shells
Terms and levels for e.c. 1s22s22p13p1?

L = 2,1,0;
2,1,0 For each L; S=1 or 0
Terms: 3D,1D, 3P, 1P, 3S, 1S
Levels for 3D: 3D3, 3D2, 3D1; Levels for 1D: 1D2
Levels for 3P: 3P2, 3P1, 3P0; Levels for 1P: 1P1
Levels for 3S: 3S1; Levels for 1S: 1S0

atoms: Electrons in same sub-shells
(Example: Carbon)
Terms and levels for e.c. 1s22s22p2?
This case is slightly complicated. Since both the electrons are in the
same p-type sub-shell, Pauli principle will restrict the spin
orientations – paired electrons cannot have parallel spins.
First we note that the number of states (possible electronic

arrangements) for the e.c. = 6C2 = 15

atoms: Example – ground electronic
configuration of Carbon atom
Terms and levels for e.c. 1s22s22p2: (Continued)
We will first collect all possible electronic distributions in spin-orbitals of 2p
sub-shell based on the (ML,MS) values.
Two electrons in same orbital
→ Must pair up
→ Only one (anti-symmetric) spin arrangement: S=0, MS=0
Two electrons in different orbitals

→ Four spin-arrangements possible
→ Three symmetric spin-arrangements: S=1, MS=1,0,-1
→ One anti-symmetric spin-arrangement: S=0, MS=0

We will first collect all possible electronic distributions in spin-orbitals of 2p
→Only a singlet possible: (S=0, MS=0) =0
→Same value of ml for each electron
→Thus, ML= 2ml.: {ML=2,0,-2}, {S=0}
Two electrons in different orbital
→A singlet (S=0, MS=0)
=0 and a triplet (S=1, MS=1,0,-1)
=1,0,-1
→The ml values of two electrons cannot be same
→Thus, ML=ml(1)+ml(2): (2) {ML=1,1,0,0,-1,-1} {S=1,0}

Now, we redistribute the ML values according to spin-states:
S=1: ML=1,0,-1 → L=1 → the term: 3P
S=0: ML=2,1,0,0,-1,-2 → ML={2,1,0,-1,-2};{0}→ L=2,0 →The terms 1D, 1S

Degeneracy of term: (2L+1)(2S+1): 1D: 5 states, 3P: 9 states, 1S: 1 state
Levels are obtained by calculating J=L+S,L+S-1,....|L-S| for every term.
1
D → 1D2; 3
P → 3P2, 3P1, 3P0; 1
S → 1S0
The degeneracy of a given level J is (2J+1).
1
D2: 5 states, 3P2: 5 states, 3P1: 3 states, 3P0, 1 state, 1S0, 1 state.

Carbon: Ground term and ground level -
Priority : spin multiplicity > orbital multiplicity: 3
P is the ground term.
Ground level: Since the 2p sub-shell is less than half-filled, 3P0 (min J) is the
ground level.
One can analogously obtain the terms for oxygen (configuration: np4) – we get just
the same terms and levels:
1
D → 1D2; 3P → 3P2, 3P1, 3P0; 1S → 1S0;
The ground term would be 3P. However, the ordering of the levels is reversed:
ground level is 3P2.
Similarly one can see that boron and fluorine have similar terms, and the ordering
of their levels is just opposite.
Homework: Find the terms and levels of B, N, O, F. (Also try for Ti if you can).

atoms: Electrons in same sub-shells
(Example: Titanium)
Terms and levels for e.c. 1s22s22p63s23p63d24s2?
In this case, the 3d sub-shell consists of two electrons and the
remaining sub-shells are either fully filled or completely empty.
Thus, the two electrons in the 3d sub-shell only will contribute to
the non-zero angular momenta.
First we note that the number of states (possible electronic

arrangements) for the e.c. = 10C2 = 45

configuration of Titanium atom
Terms and levels for e.c. [Ca]3d2: (Continued)
We will first collect all possible electronic distributions in spin-orbitals of 3d
→ Must pair up
→ Only one (anti-symmetric) spin arrangement: S=0, MS=0
Two electrons in different orbitals

→ Four spin-arrangements possible
→ Three symmetric spin-arrangements: S=1, MS=1,0,-1
→ One anti-symmetric spin-arrangement: S=0, MS=0

We will first collect all possible electronic distributions in spin-orbitals of 3d
→Only a singlet possible: (S=0, MS=0) =0
→Same value of ml for each electron
→Thus, ML= 2ml.: {ML=4,2,0,-2,-4}, {S=0}
Two electrons in different orbital
→A singlet (S=0, MS=0) =0
and a triplet (S=1, MS=1,0,-1)
=1,0,-1
→The ml values of two electrons cannot be same
→Thus, ML=ml(1)+ml(2): (2) {ML=3,2,1,1,0,0,-1,-1,-2,-3}
{S=1,0}

Now, we redistribute the ML values according to spin-states:
S=1: ML=3,2,1,1,0,0,-1,-1,-2,-3
→ ML={3,2,1,0,-1,-2,-3};{1,0,-1} S=1: L=3,1 → the terms: 3F, 3P
S=0: ML=4,3,2,2,1,0,0,0,-1,-2,-2,-3,-4
→ ML={4,3,2,1,0,-1,-2,-3,-4};{2,1,0,-1,-2},{0}→ L=4,2,0 →The terms 1G, 1D, 1S
Degeneracy of term: (2L+1)(2S+1):

1G: 9 states; 1D: 5 states; 1S: 1 state; 3F: 21 states; 3P: 9 states
(Total states: 9+5+1+21+9 = 45)


We have obtained the terms:
1
G (9 states), 3F (21 states), 1D (5 states), 3P (9 states) and 1S (1 state)
Levels are obtained by calculating J=L+S,L+S-1,....|L-S| for every term.
1
G → 1G4; 3
F → 3F4, 3F2, 3F2; 1
D → 1D2;
3
P → 3P2, 3P1, 3P0; 1
S → 1S0
The degeneracy of a given level J is (2J+1).
1
G4: 9 states, 3
F4: 9 states, 3F3: 7 states, 3F2: 5 states, D2: 5 states,
1
3
P2: 5 states, 3P1: 3 states, 3P0, 1 state, 1
S0, 1 state.

Titanium: Ground term and ground level -
1. spin multiplicity 3
F or 3P is the ground term.
2. orbital multiplicity: 3F is the ground term
Ground level: Since the 3d sub-shell is less than half-filled, 3F2 (min J) is the
ground level.
One can analogously obtain the terms for nickel (configuration: d8) – we get just the
same terms and levels.
The ground term would be 3F. However, the ordering of the levels is reversed:
ground level is 3F4.

atoms: General procedure
1. Broadly classify the distributions into sets of paired and unpaired electrons and
hence, identify the spin-multiplicities of the configurations in each set.
2. Identify all the possibilities of distribution of electrons in a given set and hence,
identify the ml values of each electron and hence, the possible ML values. Do this for
each set.
3. Collect together the ML values according to total spin quantum number, S.
4. Identify possible L values by grouping various ML’s: ML=-L...L for each, and
depending on the possible S values, find identify the terms.

5. The degeneracy of each term is (2L+1)(2S+1).
6. Spin-orbit coupling: Find J for each term: J=L+S...|L-S|;
7. Degeneracy of level= 2J+1.
Lowest energy terms and levels
The lowest energy terms and levels are obtained by applying Hund's three rules of
maximum multiplicity.
1. The first rule says that the lowest term would be the one with maximum spin
multiplicity.
2. The second rule says that if two or more terms have the highest spin multiplicity,
then among them, the term with maximum orbital multiplicity (quantum no. L) will
lie the lowest.
3. The third rule says about the ordering of levels of the lowest energy term. If the
sub-shell is less than half full, the level with smallest value of J lies the lowest in
energy. If the sub-shell is greater than half full, the level with highest value of J lies
the lowest in energy. (This rule can be easily applied only when there is a single
incompletely filled sub-shell. For multiple incomplete sub-shells, the situation is
rather complicated).

Determining Ground term and level
alone
If one wants to obtain the term and level only for ground (or the
lowest) state, then the same can be obtained very easily without
calculating the other possible terms and levels.
To get the ground (or the lowest energy) term for a configuration,
arrange the electrons in the subshell with leading to maximum spin
multiplicity. Calculate the maximum value of ML that can be
possible for this configuration which will be same as the L for the
ground term.
The lowest level can be obtained using the Hund's third rule.
e.g. nitrogen: 1s22s22p3: ML=0 → L=0; S=3/2 → Term is 4S, level
is 4S3/2.

Spin-orbit coupling – atomic spectra
The doublet D ‘line’ in the emission spectrum of Na:

The lowest excited electronic configuration of sodium is [Ne]3p 1. The term is
P with two levels: 2P3/2 and 2P1/2, respectively. The term corresponding to
2
electronic configuration is [Ne]3s1 is 2S with the only level, 2S1/2.
The doublet is obtained because of the the two transitions:

2
P3/2 → 2S1/2 (589.0 nm) and 2P1/2 → 2S1/2 (589.6 nm)
Analogously, the Lyman α (2p→1s) in H-atomic emission spectrum is also a

doublet as a consequence of spin-orbit coupling.

Selection rules of atomic spectra
Taking into consideration the spin-orbit interactions in many-

electron atoms, following are the selection rules for the atomic
spectra
ΔL=0, ±1,
ΔS=0,
ΔJ=0, ±1, (however, the J=0↔J=0 transition is forbidden)

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BITS Pilani

CHEM F111 General Chemistry Lecture 01

Sir Issac Newton (1642-1726)

Joseph Louis Lagrange (1736-1813)

John Dalton – Concept of atoms (1803)

Amedeo Avogadro – Concept of molecules (1811)

Sir J. J. Thomson – Concept of electron (1897)

Millikan – Charge of elementary particles (1909)

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In the light of the topics:

we will learn that

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Perfectly black-body: A body that absorbs and emits radiations of all

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Emittance M: Total power emitted per unit area

Weins’ displacement law:

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Attempts to explain BBR:

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Planck found that with h=6.626 x 10-34Js,

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DIY: Plot the energy density as a function of wavelength for different

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• Threshold frequency ν0 characteristic of the metal below which there

Intensity being proportional to the number of photons cannot bring about

CHEM F111 General Chemistry Lecture 02

• Planck black body radiation

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• Electron (mass m and charge –e)

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•Any kind of motion can be excited to any arbitrary value of the

Davisson and Germer performed electron diffraction

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Clinton Joseph Davisson (left) and

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Macroscopic objects are so massive that the de Broglie

Homework: Use de Broglie hypothesis to justify the Bohr's

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Experiment with electrons, photons etc. :

wave-like, depending on the nature of the observation

answered only if the experiment being performed is capable of answering. If

Heisenberg’s uncertainty principle is the consequence

It is impossible to specify simultaneously, with arbitrary precision, (a given

For energy time uncertainty measurement, the inequality is slightly different:

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Definite wavelength → definite momentum, but since wave

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Superposition of waves, uncertainty in both position and

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Particle with precisely defined position/ Wavelength

CHEM F111 General Chemistry Lecture 03

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•Impossible to exactly and simultaneously measure position and

BITSPilani, Pilani Campus

Example – One dimensional one-particle system

The particle is confined to the region where the wavefunction is

BITSPilani, Pilani Campus

Example – One dimensional one-particle system

The particle is confined to the region where the wavefunction is

Example – One dimensional one-particle system