Quantum Chemistry and Spectroscopy

Sem-IV (general course)

Physical Chemistry

Biswajit Halder

Particle in One Dimensional Box

Quantisation of motion
If a stretched string is rigidly clamped at both ends then it will have fixed length. We
can only set up standing wave on it. This standing wave can only have definite and discrete frequencies
(fundamental mode and overtones). So quantisation of motion arises due to confining of the wave at
definite region of space. This concept is applied to all kind of waves including matter wave. For matter
wave, dealing with energy (E) is easier then frequency because of Schrodinger equation.
Confinement Principle
An electron of an atom held within the atom by columbic interaction between electron
and nucleus and it can exist only in a set of discrete energy states. This electron is not a free electron. On
the other hand an electron moving in positive x direction and subject to no net force is a free particle that
can have any reasonable value. According to confinement principle, Confinement of a wave leads to
quantisation – that is, to the existence of discrete states and discrete energies.(Halliday, Resnick and
Walker – Fundamentals of Physics, 6th edition . (page 980).

Particle in one dimensional box

A particle of mass m is confined in region along x direction between x = 0 and x = a.
suppose, the particle experience no potential energy, V(x) = 0 inside this region, ψ(x) is the wave
function associate with it . This is called the problem of a free particle in one dimensional box. This
simple model has a crude application to the π electron in linear conjugated hydrocarbon. Schrodinger
equation for this problem is

(d2/dx2 )ψ(x) + (2mE/ћ2) ψ(x) = 0 0≤x≤a

So it is a free particle , particle is not subject to any kind of force other than a uniform potential field
which is taken as zero. There is no potential barrier to restrict the motion of the particle.
(d2/dx2 )ψ(x) + (2mE/ћ2) ψ(x) = 0
equation of this type canbe generally written as

(d2y/dx2 )+ ω2y = 0
General solution of this equation is y(x) = c1eiωx + c2e-iωx
Or y(x) = A cosωx + B sin ωx
The probability of finding the particle outside the region is zero. Ψ(x) is continuous inside this box of
length a. Therefore ψ(0) = ψ(a) = 0 is the boundary for this problem.
Now the discrete wave patterns (in which the string can oscillate) are those for which the length a of the
string is equal to integral multiple of half wave length. Where n indicates state of the oscillating string.
For particle wave n is called quantum number.
a = (n λ /2)
The general solution of Schrodinger equation for this problem is
ψ (x) = A coskx + B sin kx
where k = (2mE)1/2 / ћ
Applying boundary condition
ψ (0) = 0 implies A = 0.
The second boundary condition gives
ψ (a) = B sin kx = 0
So ka = nπ where n = 1,2,3, ……
Now ψ (x) = A sin kx = A sin (nπx/a)

Putting k = nπ/a we find that En = (h2/8ma) n2 n = 1,2,3, ……

So energy of the particle is quantised. (So the introduction of integral arises in the same
natural way as in vibrating string for which the number of nodes is integral). The quantum
state for lower possible energy state E1 is called ground state. It can be changed to an excited
state only if an external source provides the energy that is required for this transition. If
confined electron is to absorb a photon, the energy hν of the photon must be equal to the
energy difference ΔE between initial energy level to next higher energy level.
ΔE = hν = En+1 – En
(Though absorption and emission can applied to the electron traps. But in reality it cannot be
applied to one dimensional case because photo absorption and emission require conservation
of angular momentum.)

Zero point energy

E1 is the ground energy state for particle in one dimensional box. Electron will
occupy this state unless no energy is supplied to excite the electron in its next higher energy
state. If ground state energy was zero it would have |Ψ|2 = 0. So there cannot be any electron
inside the one dimensional box. So it is an important conclusion that any confined system
cannot exist in state with zero energy. They always have a certain minimum energy
(E =h2/8ma here) called zero point energy.

Normalisation of the Wave function

According to the Born approximation
p(x) = Ψn*(x) Ψn(x) dx
is the probability that a particle is locate between x and x + dx. Particle is confined in space
between x=0 and x=a so the probability of the particle lies between x=0 and x=a must be
unity.
ʃ0aΨn*(x) Ψn(x) dx = ʃ0 aA2 sin2 (nπx/a) dx = 1
The wave function that satisfy this equation is said to be normalised.
2
Ψn(x) = sin2 (nπx/a)
𝑎
2
A= is called normalisation constant.
𝑎

Postulate of quantum Mechanics

Postulate 1 A state of a system is defined by a mathematical function ψ, called the state
function or the wave function which determines all measurable quantities of the system at
that state. Ψ is a function of coordinates of all the particles and also time. Wave function Ψ is
interpreted physically as |Ψ|2 being the probability density for finding the particles at given
locations in space. For one particle system |Ψ|2 is probability of finding the particle at time t
with coordinates x1 to x1+dx, y1 to y1+dy, and z1 to z1+dz in a tiny volume of dimension
dxdydz .
Pr(x1< x < x1+dx, y1< y < y1+dy, z1 < z < z1+dz)
= |Ψ (x1, y1, z1, t) |2 dxdydz
Ψ is a complex quantity so value of |Ψ|2 = Ψ * Ψ where Ψ * is complex conjugate of Ψ. For
one particle one dimensional (say in x direction) system, the probability of finding the
particle somewhere in x direction must by 1. So ʃ-α+α |Ψ|2 dx= 1.
Postulate 2to every physically measurable or observable quantity like position , momentum ,
energy etc of a system there corresponding a linear operator in quantum mechanics.

An operator is a rule for transforming a given function into another function. SupposÂ
symbolise an operator that transforms a function f(x) into g(x) then  f(x) = g(x).

(operator) (function) = (new function)

In quantum mechanics, each physical property of a system has a corresponding operator.(list

of quantum mechanical operator see McQuarrie , sec 4.2) . When an operator is applied to a
function gives the function back but multiplied by the constant c , Â f = c f then f is called an
eigen function of  with eigen value c .
The operators that corresponds to physical entities in quantum mechanics are linear.
 (f + g) =  f +  g and  (cf) = c  f
If the system’s state function ψ happens to be an eigen function of  correspond to the
property A with eigen value c, then a measurement of A is certain to give the value c as the
result.
The average value of any physical property A in a system whose state function is ψ is
given by < A > = ψ*Â ψ dτ
Where  is the operator for property A and integral is done over whole space.

Commutation relation
The product of two operators is define by operating them on a function. Suppose a and b are
two operators and f(x) is a function. Ab f(x) indicates that b is operating upon f(x) ,
producing new function and then a is operating on that new function. Consider two
𝑑 𝑑
fundamental operators x and p, xpf(x) = x(-iћ) 𝑑𝑥 f(x) and pxf(x) = (-iћ) 𝑑𝑥 𝑥f(x) = (-iћ)f(x) -
𝑑
x(-iћ) 𝑑𝑥 f(x) and (xp – px)f(x) = iћf(x) if f(x) is differentiable. So x and p non commutating.
It is customary to use [Ab ]= ab – ba and this is called commutator of a and b. if [Ab]= 0 then
a and b commute with each other . commmutator operator have simultaneous eigenstates.
These cannot be measured simultaneously.

Postulate 3:The only possible value that can be observed of a physical properties like energy
, angular momentum etc. of a system in a stationary state are the eigenvalues of the operator
of the type  ψ = cψ
then ψ is wave behaved function called an eigen function of oparetor  of the observable
obtained by Schrodinger prescription with eigen value c .
Postulate 3. In any measurement of the observable associated with

Postulate 4:If a system is in a state described by a normalized wave function Ψ, then the
average value of the observable corresponding to  is given by
< A > = (ʃψ*Â ψ dτ)/ʃψ*ψ dτ
When the wave function is normalised ʃψ*ψ dτ= 1
( integrations are done over all space of wave function)

Postulate 5 The wave function or state function of a system evolves in time according to the
𝜕
time-dependent Schrodinger equation Ĥ ψ = (ih/2π)𝜕𝑡 ψ

Spectroscopy
In 1900 Max Planck explained the phenomenon “Black Body Radiation” by concluding that
light must be quantised.
When light enters the cavity with a small opening, it is reflected throughout the internal
surface. The light that escapes is representative of the internal temperature of the cavity.
Classical theory predicts that the intensity of the light that escapes increases with the
frequency of the light.Classically, the intensity of the light increases to infinity as the
temperature increases. Experimentally, the maximum intensity shifts to the blue as
temperature increases.
ρ(ν)d ν = [ (8 πh)/c3 ] ν3[1/(e(hv/ kT) -1)]
Plank’s equation corrected for classical failure by stating that energy can only be transferred
in a finite minimum quantity.
In 1905 Albert Einstein used Planck’s Law to explain the Photoelectric Effect.
When light strikes the surface of certain metals, electrons are ejected. The ejected electrons
produce a current that proportional to their number.
It is found that the current produced follows the light intensity. And there is a frequency
dependence, below which, no electros are ejected.
1905 –Einstein: oscillators in light source can only have quantized energies
E = nhν (n = 0,1,2,3,…).
As oscillators change their energy from nhν to (n-1)hν, emit radiation of frequencyv and
energyhv (photon). If the photons energy is more than Φthen an electron is ejected:
KE (electron) = E (photon) – Φ = ½mev2
The Wave-like Nature of a Particle

Louis de Brogliein response to Planck & Einstein’s assertion that light was “particle-
like”(photon) stated that small particles moving fast could exhibit a characteristic
wavelength.
E = mc2 so, E= hν = mc2(it can be conclude that particles have a wave length)
h(ν/c) = mc = p momentum , (it can be concluded that light have a mass)
Again (ν/c) = (1/λ)
p = (h/λ)
(Example 1: What is the de Brogliewavelength of an electron traveling at 0.1 c (c=speedof
light)? c= 3.00x108 m/s me = 9.1x10-31 kg, h = 6.63x10-34 J s

λ = (h/p) = (h/mc) = (6.63x10-34)/[(3.00x108)(0.1).(9.1x10-31)]

= 2.4x10-11 m = 0.24 Å (on the order of atomic dimensions)

Example 2: What is the de Brogliewavelength of a 1 gram marble traveling at 10 cm/s

(given , h = 6.63x10-34 J s)
λ = (h/p) = (h/mc) = (6.63x10-34)/[(0.1).(10-3)]
= 6.6x10-30 m = 6.6x10-20 Å (insignificant)
So, from the above discussion it can be concluded that the wavelooks like superimpose on a
particle or the electron appears as a build up of amplitude in the wave.
De Broglie showed that Bohr’s arbitrary quantum rule was natural corollary of de Broglie’s
hypothesis if one assumed that an electron in a stable Bohr orbit may be regarded as a
standing wave and thus must consist of an integral number of wave length.
Therefore
nλ = 2πr n = 1, 2, 3……..
putting the value of λ from above to de Broglie equation
λ=(2πr/n) =(h/p) or, pr = (nh/2λ) or, mvr = (nh/2π)
that is Borh quantum condition. So quantisation comes naturally if we consider the waves
associated with particles in their bound state.
Spectroscopy and its importance in chemistry
Spectroscopy measure the interaction of matter with radiation. It deals with the observation of
the ways atoms or molecules exchange energy with the outer world. According to Borh’s
resonance condition spectra aries from absorption and emission of definite quanta of radiation
when transitions occur between two energy levels ( E1andE2).
| E2 – E1| = hν = (hc/λ) = hcῡ
Where h = Planck constant , ν, λ , ῡ are frequency , wave length, and wave number of the
emitted and absorbed radiation. By means of this interpretation of the energy level based on
quantum mechanics details information can be derived concerning structure of atoms and
molecules or crystal,arrangement of ions in moleculesor crystals, shape of the molecules,
dissociation energies etc. analysis of kinetics of photochemical reactions requires
understanding of photochemical process that can occur when light is absorbed by chemical
reactants.

Interaction of electromagnetic radiation with matter

An atom can interacts with electromagnetic radiation and its electronic state may change
thereby giving spctra. This type of spectroscopy is known as electronic spectra owing to the
fact that outer most orbital electron transits from one energy level to another energy level. A
molecule also can absorb or emit energy during its transition between two different electronic
leveks. A molecule can changes its energy in two other possible ways, which do not occur in
atoms. The vibration of atoms within the molecules and rotational states of the molecules.
When electron is expelled from inner most energy level of the atom X rays generate.
Vibrational and rotational levels are also quantised so certain distinct of vibrational and
rotational levels are permissible. The wavelength of the absorption and emission radiation is
described by the difference between the energy levels. Generally rotational spectra are found
in the microwave and far infra-red region, for this a molecule must have permanent dipole
moment. Vibrational – rotational spectra are found in mid and near infra – red region and
electronic spectra in visible and ultraviolet region.
Type of spectra
A spectrum (sequence of ordered things, here light) which consists of bright lines produced
by the emission of electromagnetic radiation called emission spectra, and the dark lines
produced by absorption of incident light is known as absorption spectrum. The spectra
generally consist of closely spaced lines packed into groups are called bands.
Radiation Frequency Wave Molecular energy Information obtained
Region range(Hz) number levels involved
( cm-1)
Radio 106 to 109 3x10-1 to Reversal of spin of Structural information of
frequency 3x10-4 nuclear or electrons molecules
Microwave 109 to 0.3 to 3 Rotation of heavy Inter molecular distance and
11
10 molecules dipole moment
Far Infra- 1011 to 3 to 300 Rotation of light and Inter molecular distance and
13
red 10 vibration of heavy bond force constant
mole cules
Mid and 1013 to 300 to Vibration-rotation of Inter molecular distance and
near infra- 1014 3000 light molecules bond force constant
red
Visible 1014 to 3000 to Electronic transition Bond dissociation energy
and Ultra 1016 30000
violet
X – rays 1016 to 3x105 to Energy change of Structure of crystal
1018 3x107 inner electron
Γ - rays 1018 7
to 3x10 to Rearrangement of -
1020 3x109 nucleus

When the excitation energy is small, transition between rotational levels are possible and
spectral lines are appeared in microwave and far infra – red region. Rotational spectra
provide information about the moment of inertia (distribution of mass around an axis),
interatomic distances, bond angle and dipole moment.If excitation is sufficient , transition
occur between vibrational levels ( vibrational transition is associate with number of rotational
transition) which gives information about vibrational frequency and force constant of the
bond.