UNIT-1

INTRODUCTION
Quantum Chemistry
In the late seventeenth century, Isaac Newton discovered classical mechanics, the laws of motion
of macroscopic objects. In the early twentieth century, physicists found that classical mechanics
does not correctly describe the behavior of very small particles such as the electrons and nuclei of
atoms and molecules. The behavior of such particles is described by a set of laws called quantum
mechanics.

Quantum chemistry applies quantum mechanics to problems in chemistry. The influence of

quantum chemistry is evident in all branches of chemistry. Physical chemists use quantum
mechanics to calculate (with the aid of statistical mechanics) thermodynamic properties (for
example, entropy, heat capacity) of gases; to interpret molecular spectra, thereby allowing
experimental determination of molecular properties (for example, molecular geometries, dipole
moments, barriers to internal rotation, energy differences between conformational isomers); to
calculate molecular properties theoretically; to calculate properties of transition states in chemical
reactions, thereby allowing estimation of rate constants; to understand intermolecular forces; and
to deal with bonding in solids.

Quantum mechanics determines the properties of nanomaterials (objects with at least one
dimension in the range 1 to 100 nm), and calculation methods to deal with nanomaterials are being
developed. When one or more dimensions of a material fall below 100 nm (and especially below
20 nm), dramatic changes in the optical, electronic, chemical, and other properties from those of
the bulk material can occur.

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 UNIT -2
EXPERIMENTAL FOUNDATION OF QUANTUM THEORY
Electromagnetic Energy
Visible light and other forms of electromagnetic radiation play important roles in chemistry, since
they can be used to infer the energies of electrons within atoms and molecules. Much of modern
technology is based on electromagnetic radiation.
 For example, radio waves from a mobile phone,
 X-rays used by dentists/physicians,
 the energy used to cook food in your microwave,
 the radiant heat from red-hot objects, and
 the light from your television screen are forms of electromagnetic radiation that all
exhibit wavelike behavior.

Characteristics of Light
Waves
A wave is an oscillation or periodic movement that can transport energy from one point in space
to another. Common examples of waves are all around us.
 Shaking the end of rope transfers energy from your hand to the other end of the rope,
 dropping a pebble into a pond causes waves to ripple outward along the water's surface,
 The expansion of air that accompanies a lightning strike generates sound waves (thunder)
that can travel outward for several miles.

In each of these cases, kinetic energy is transferred through matter (the rope, water, or air) while
the matter remains essentially in place.Waves need not be restricted to travel through matter.
Electromagnetic waves consist of an electric field oscillating in step with a perpendicular magnetic
field, both of which are perpendicular to the direction of travel. These waves can travel through a
vacuum at a constant speed of 2.998 × 108 m/s, the speed of light (denoted by c). All waves,
including forms of electromagnetic radiation, are characterized by two interdependent variables: -
1. Wavelength (denoted by λ, the lowercase Greek letter lambda), wavelength is the

distance between two consecutive peaks or troughs in a wave (measured in meters in the SI
system). Electromagnetic waves have wavelengths that fall within an enormous range wavelengths
of kilometers (103 m) to picometers (10-12 m) have been observed.

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2. Frequency (denoted by ν, the lowercase Greek letter nu), is the number of wave cycles

that pass a specified point in space in a specified amount of time (in the SI system, this is measured
in seconds). A cycle corresponds to one complete wavelength. The unit for frequency, expressed
as cycles per second [s-1], is the hertz (Hz). Common multiples of this unit are megahertz, (1 MHz
= 1×106 Hz) and gigahertz (1 GHz = 1×109 Hz).

3. Amplitude is another type of variable that corresponds to the magnitude of the wave's
displacement and so, this corresponds to the half of the height between the peaks/crest and troughs.
The amplitude is related to the intensity of the wave, which for light is the brightness, and for
sound is the loudness.

Figure 2.1: One-dimensional sinusoidal waves show the relationship among wavelength,
frequency, and speed.

Wavelength and frequency are inversely proportional: As the wavelength increases, the frequency
decreases. The wave with the shortest wavelength has the highest frequency. The electromagnetic
spectrum, the range of all types of electromagnetic radiation and colors of visible light has specific
frequencies and wavelengths associated with them.

 For example, radio waves are usually specified as frequencies (typically in units of MHz),
while the visible region is usually specified in wavelengths (typically in units ofnm or
angstroms)

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Figure 2.2: Portions of the electromagnetic spectrum are shown in order of decreasing frequency
and increasing wavelength.

2.1 Black body Radiation

In the 1890s, physicists measured the intensity of light at various frequencies emitted by a heated
blackbody at a fixed temperature, and did these measurements at several temperatures. A
blackbody is an object that absorbs all light falling on it.
In 1896, the physicist Wien proposed the equation for the dependence of blackbody radiation on
light frequency and blackbody temperature: Wien’s formula gave a good fit to the blackbody
radiation data available in 1896, but his theoretical arguments for the formula were considered
unsatisfactory.

In 1899–1900, measurements of blackbody radiation were extended to lower frequencies than

previously measured, and the low-frequency data showed significant deviations from Wien’s
formula. These deviations led the physicist Max Planck to propose in October. Planck assumed
the radiation emitters and absorbers in the blackbody to be harmonically oscillating electric
charges (“resonators”) in equilibrium with electromagnetic radiation in a cavity. He assumed that
the total energy of those resonators whose frequency is n consisted of N indivisible “energy
elements,” each of magnitude hn, where N is an integer and h (Planck’s constant) was a new
constant in physics. Planck distributed these energy elements among the resonators. In effect, this
restricted the energy of each resonator to be a whole-number multiple of hv (although Planck did

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not explicitly say this). Thus the energy of each resonator was quantized, meaning that only
certain discrete values were allowed for a resonator energy. Planck’s theory showed that a =
2ph>c2 and b = h>k, where k is Boltzmann’s constant. By fitting the experimental blackbody
curves,
Planck found h = 6.6 * 10-34 J s-1.

The concept of energy quantization is in direct contradiction to all previous ideas of physics.
According to Newtonian mechanics, the energy of a material body can vary continuously.
However, only with the hypothesis of quantized energy does one obtain the correct blackbody-
radiation curves.

2.2 Photoelectric Effect

The classical theory to be resolved concerned the photoelectric effect; which had been observed
that electrons could be ejected from the clean surface of a metal when light having a frequency
greater than some threshold frequency was shone on it. Surprisingly, the kinetic energy of the
ejected electrons did not depend on the brightness of the light, but increased with increasing
frequency of the light. Since the electrons in the metal had a certain amount of binding energy
keeping them there, the incident light needed to have more energy to free the electrons. According
to classical wave theory, a wave's energy depends on its intensity (which depends on its amplitude),
not its frequency. One part of these observations was that the number of electrons ejected within
in a given time period was seen to increase as the brightness increased.

In 1905, Albert Einstein was able to resolve the paradox by incorporating Planck's quantization
findings into the discredited particle view of light.
 Planck had postulated “blackbody radiation could be applied to the light in the
photoelectric effect so that the light striking the metal surface should not be viewed as a
wave, but instead as a stream of particles (later called photons) whose energy depended
on their frequency.”
 Electrons were ejected when hit by photons having sufficient energy (a frequency
greater than the threshold).
 The greater the frequency, the greater the kinetic energy imparted to the escaping
electrons by the collisions.
 E = hν (or, in terms of wavelength using c = νλ, E = hc/λ ).
With Einstein's findings, the nature of light took on a new air of mystery.
 Although many light phenomena could be explained either in terms of waves or particles,

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certain phenomena, such as the interference patterns obtained when light passed through
a double slit, were completely contrary to a particle view of light, while other
phenomena, such as the photoelectric effect, were completely contrary to a wave view of
light.
 Somehow, at a deep fundamental level still not fully understood, light is both wavelike
and particle-like. This is known as wave-particle duality.

 E = hv

Figure 2.3: Photons with low frequencies do not have enough energy to cause electrons to be
ejected via the photoelectric effect
Example

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 2. 3. Rutherford model of the atom
Starting in 1909, Rutherford, Geiger, and Marsden repeatedly passed a beam of alpha particles
through a thin metal foil and observed the deflections of the particles by allowing them to fall on
a fluorescent screen. Alpha particles are positively charged helium nuclei obtained from natural
radioactive decay. Most of the alpha particles passed through the foil essentially undeflected, but,
surprisingly, a few underwent large deflections, some being deflected backward. To get large
deflections, one needs a very close approach between the charges, so that the Columbic repulsive
force is great. Hence Rutherford concluded that such large deflections could occur only if the
positive charge were concentrated in a tiny, heavy nucleus.

The chemical properties of atoms and molecules are determined by their electronic structure, and
so the question arises as to the nature of the motions and energies of the electrons. Since the nucleus
is much more massive than the electron, we expect the motion of the nucleus to be slight compared
with the electrons’ motions.

In 1911, Rutherford proposed his planetary model of the atom in which the electrons revolved
about the nucleus in various orbits, just as the planets revolve about the sun. However, there is a
fundamental difficulty with this model. According to classical electromagnetic theory, an
accelerated charged particle radiates energy in the form of electromagnetic (light) waves. An
electron circling the nucleus at constant speed is being accelerated, since the direction of its
velocity vector is continually changing. Hence the electrons in the Rutherford model should
continually lose energy by radiation and therefore would spiral toward the nucleus. Thus,
according to classical (nineteenth-century) physics, the Rutherford atom is unstable and would
collapse.

2.4 Bohr model of the atom

Niels Bohr in 1913, when he applied the concept of quantization of energy to the hydrogen atom.
Bohr assumed that the energy of the electron in a hydrogen atom was quantized, with the electron
constrained to move only on one of a number of allowed circles. When an electron makes a
transition from one Bohr orbit to another, a photon of light whose frequency v satisfies. is absorbed
or emitted, where Eupper and Elower are the energies of the upper and lower states (conservation of
energy). he got agreement with the observed hydrogen spectrum.

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  However, attempts to fit the helium spectrum using the Bohr theory failed. Moreover, the
theory could not account for chemical bonds in molecules.

The failure of the Bohr model arises from the use of classical mechanics to describe the electronic
motions in atoms. The evidence of atomic spectra, which show discrete frequencies, indicates that
only certain energies of motion are allowed; the electronic energy is quantized.

 Since Bohr’s model involved only a single electron, it could also be applied to the single
electron ions He+, Li2+, Be3+, and so forth, which differ from hydrogen only in their
nuclear charges, and so one-electron atoms and ions are collectively referred to as
hydrogen-like atoms. The energy expression for hydrogen-like atoms is a generalization of
the hydrogen atom energy, in which Z is the nuclear charge (+1 for hydrogen, +2 for He,
+3 for Li, and so on) and k has a value of 2.179 × 10–18 J.\

Example 6.3

 Calculating the Energy of an Electron in a Bohr Orbit

1. Early researchers were very excited when they were able to predict the energy of an
electron at a particular distance from the nucleus in a hydrogen atom. If a spark promotes
the electron in a hydrogen atom into an orbit with n = 3, what is the calculated energy, in
joules, of the electron?
Solution: The energy of the electron is given by this equation:
The atomic number, Z, of hydrogen is 1; k = 2.179 × 10–18 J; and the electron is
characterized by an n value of 3. Thus,

Calculating the Energy and Wavelength of Electron Transitions in a one electron (Bohr)
System
2. What is the energy (in joules) and the wavelength (in meters) of the line in the spectrum of
hydrogen that represents the movement of an electron from Bohr orbit with n = 4 to the
orbit with n = 6? In what part of the electromagnetic spectrum do we find this radiation?

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 Solution: In this case, the electron starts out with n = 4, so n1 = 4. It comes to rest in the n =
6 orbit, so n2 = 6. The difference in energy between the two states is given by this expression:

ii) This energy difference is positive, indicating a photon enters the system (is absorbed) to
excite the electron from the n = 4 orbit up to the n = 6 orbit. The wavelength of a photon
with this energy is found by the expression E = ℎc/λ. Rearrangement gives:

2.5 The Wave properties of Particles

Louis de Broglie suggested in 1923 that the motion of electrons might have a wave aspect; that an
electron of mass m and speed v would have a wavelength associated with it, where p is the linear
momentum.

 Thus electrons behave in some respects like particles and in other respects like waves.
(“wave–particle duality” of matter (and of light).
 Although both photons and electrons show an apparent duality, they are not the same kinds
of entities. Photons travel at speed c in vacuum and have zero rest mass; electrons always
have v < c and a nonzero rest mass. Photons must always be treated relativistically, but
electrons whose speed is much less than c can be treated nonrelativistically.

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 2. 6. The Uncertainty Principle
Heisenberg’s uncertainty principle states that it is impossible to measure or calculate exactly
both the position and the momentum of an object. This principle is based on the wave-particle
duality of matter. Although Heisenberg’s uncertainty principle can be ignored in the macroscopic
world (the uncertainties in the position and velocity of objects with relatively large masses are
negligible), it holds significant value in the quantum world. Since atoms and subatomic particles
have very small masses, any increase in the accuracy of their positions will be accompanied by an
increase in the uncertainty associated with their velocities. Another implication of the uncertainty
principle is that it is impossible to accurately measure the energy of a system in some finite amount
of time.

 The wavelength l is given by the de Broglie relation wavelength = h>p, so Δx Δp = h. Since

the uncertainties have not been precisely defined, the equality sign is not really justified.
Instead we write

indicating that the product of the uncertainties in x and px is of the order of magnitude of Planck’s
constant.

UNIT 3
The Schrödinger Equation
3.1 The Time-Dependent Schrödinger Equation
Classical mechanics applies only to macroscopic particles. For microscopic “particles” we require
a new form of mechanics, called quantum mechanics. We now consider some of the contrasts
between classical and quantum mechanics. For simplicity a one-particle, one-dimensional system
will be discussed.
In classical mechanics the motion of a particle is governed by Newton’s second law

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where F is the force acting on the particle, m is its mass, and t is the time; a is the acceleration,

The classical-mechanical potential energy V of a particle moving in one dimension is defined to

satisfy

The word state in classical mechanics means a specification of the position and velocity of each
particle of the system at some instant of time, plus specification of the forces acting on the particles.

To describe the state of a system in quantum mechanics, we postulate the existence of a function
wave function of the particles’ coordinates called the state function or wave function. Since the
state will, in general, change with time, Ψ is also a function of time. For a one-particle, one-
dimensional system, we have Ψ = Ψ (x, t).

 The wave function(Ψ) contains all possible information about a system, so instead of
speaking of “the state described by the wave function ,” we simply say “the state Ψ.”
 To find the future state of a quantum-mechanical system from knowledge of its present
state, we want an equation that tells us how the wave function changes with time. For a
one-particle, one-dimensional system, this equation is postulated to be

where the constant h (h-bar) is defined as

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The concept of the wave function and the equation governing its change with time were discovered
in 1926 by the Austrian physicist Erwin Schrödinger (1887–1961). In this equation, known as the
time-dependent Schrödinger equation (or the Schrödinger wave equation), i = square of root -1,
m is the mass of the particle, and V (x, t) is the potential energy function of the system.

3.2 The Time-Independent Schrödinger Equation

The time-dependent Schrödinger equation (1.13) is formidable looking. Fortunately, many
applications of quantum mechanics to chemistry do not use this equation. Instead, the simpler time-
independent Schrödinger equation is used.

……..(1)

The time-independent Schrödinger equation (1) for a single particle of mass m moving in one
dimension.

The wave function is complex, but the quantity that is experimentally observable is the probability
density Ψ (x, t). The square of the absolute value of a complex quantity is given by the product of
the quantity with its complex conjugate, the complex conjugate being formed by replacing i with
–i wherever it occurs.

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