Submitted By : Awais ur Rehman
Submitted to : Dr. Hanif Sir
Class : Mphil-1st
Subject : Quantum Mechanics
Roll. No ______________
Assignment Topics : Bohr Model and
concept of principal quantum number ,
Planck quantization theory.
Overview of the Bohr Model
NeilBohr proposed the Bohr Model of the
Atom in 1915. Because the Bohr Model is a
modification of the earlier Rutherford Model,
some people call Bohr's Model the
Rutherford-Bohr Model. The modern model
of the atom is based on quantum mechanics.
The Bohr Model contains some errors, but it
is important because it describes most of the
accepted features of atomic theory without all
of the high-level math of the modern version.
Unlike earlier models, the Bohr Model
explains the Rydberg formula for the spectral
emission lines of atomic hydrogen.
Overview of the Bohr Model
The Bohr Model is a planetary model in which
the negatively charged electrons orbit a
small, positively charged nucleus similar to
the planets orbiting the sun (except that the
orbits are not planar). The gravitational force
of the solar system is mathematically akin to
the Coulomb (electrical) force between the
positively charged nucleus and the negatively
charged electrons.
Main Points of the Bohr Model
Electrons orbit the nucleus in orbits that have
a set size and energy.
The energy of the orbit is related to its size.
The lowest energy is found in the smallest
orbit.
Radiation is absorbed or emitted when an
electron moves from one orbit to another.
Bohr Model of Hydrogen
The simplest example of the Bohr Model is for the
hydrogen atom (Z = 1) or for a hydrogen-like ion (Z
> 1), in which a negatively charged electron orbits a
small positively charged nucleus. Electromagnetic
energy will be absorbed or emitted if an electron
moves from one orbit to another. Only certain
electron orbits are permitted. The radius of the
possible orbits increases as n2, where n is
the principal quantum number. The 3 → 2 transition
produces the first line of the Balmer series. For
hydrogen (Z = 1) this produces a photon having
wavelength 656 nm (red light).
Bohr Radius
To explain line spectra, Neils Bohr proposed that the
angular momentum of the electrons orbiting the
atom is quantized:
mvr = nh/2pi
where m is the mass of the electron, r is the radius of
the orbit, and v is the orbital speed of the electron.
The electron is experiencing uniform circular motion.
The only force on it is the attractive force between
the negative electron and the positive nucleus:
kZe2/r2 = mv2/r
Therefore mv2 = kZe2/r
If you rearrange Bohr's angular momentum equation
to solve for the velocity:
v = nh/2pimr
Bohr Radius
and then plug that into the equation:
mv2 = kZe2/r you get:
mn2h2/4p2m2r2 = kZe2/r
Solving this for the radius of the nth orbit gives:
r = [h2/4p2mkZe2] n2
n
r = [5.29 x 10-11 m] n2
n
5.29 x 10-11 m is known as the Bohr radius.
So, Bohr's assumption that the angular momentum
is quantized produces the result that the radii of
the electron's allowed orbits are also quantized.
Bohr energy for Hydrogen atom
To get the electron orbital energies, we start
noting that the electron energy is the sum of
its kinetic and potential energy: En = KE + PE.
Kinetic energy is the familiar:
assuming the electron is not moving at
relativistic speeds. Potential energy for the
electron is electrical, or PE = qeV, where V is
the potential due to the nucleus, which looks
like a point charge. The nucleus has a
positive charge Zqe ; thus,
Energy for hydrogen atom
recalling an equation for the potential due to
a point charge. Since the electron’s charge is
negative, we see that:
Entering the expressions for KE and PE, we
find:
Energy for hydrogen
atom
Now we substitute rn and v from earlier
equations into the above expression for
energy. Algebraic manipulation yields:
for the orbital energies of hydrogen-like
atoms. Here, E0 is the ground-state
energy (n = 1) for hydrogen (Z = 1) and is
given by
Energy for hydrogen atom
Thus, for hydrogen:
Electron total energies are negative, since the
electron is bound to the nucleus, analogous to being
in a hole without enough kinetic energy to escape.
As n approaches infinity, the total energy becomes
zero. This corresponds to a free electron with no
kinetic energy, since rn gets very large for large n,
and the electric potential energy thus becomes zero.
Thus, 13.6 eV is needed to ionize hydrogen (to go
from –13.6 eV to 0, or unbound), an experimentally
verified number. Given more energy, the electron
becomes unbound with some kinetic energy.
Explanation of Bohr Model by diagram
Bohr Model for Heavier Atoms
Heavier atoms contain more protons in the nucleus than the
hydrogen atom. More electrons were required to cancel out
the positive charge of all of these protons. Bohr believed
each electron orbit could only hold a set number of
electrons. Once the level was full, additional electrons would
be bumped up to the next level. Thus, the Bohr model for
heavier atoms described electron shells. The model
explained some of the atomic properties of heavier atoms,
which had never been reproduced before. For example, the
shell model explained why atoms got smaller moving across
a period (row) of the periodic table, even though they had
more protons and electrons. It also explained why the noble
gases were inert and why atoms on the left side of the
periodic table attract electrons, while those on the right side
lose them. However, the model assumed electrons in the
shells didn't interact with each other and couldn't explain
why electrons seemed to stack in an irregular manner.
Limitations of the Bohr Model
It violates the Heisenberg Uncertainty
Principle because it considers electrons to have
both a known radius and orbit.
The Bohr Model provides an incorrect value for
the ground state orbital angular momentum.
It makes poor predictions regarding the spectra
of larger atoms.
It does not predict the relative intensities of
spectral lines.
The Bohr Model does not explain fine structure
and hyperfine structure in spectral lines.
It does not explain the Zeeman Effect.
Refinements and Improvements to the Bohr Model
The most prominent refinement to the Bohr model was
the Sommerfeld model, which is sometimes called the
Bohr-Sommerfeld model. In this model, electrons
travel in elliptical orbits around the nucleus rather than
in circular orbits. The Sommerfeld model was better at
explaining atomic spectral effects, such the Stark
effect in spectral line splitting. However, the model
couldn't accommodate the magnetic quantum number.
Ultimately, the Bohr model and models based upon it
were replaced Wolfgang Pauli's model based on
quantum mechanics in 1925. That model was
improved to produce the modern model, introduced by
Erwin Schrodinger in 1926. Today, the behaviour of
the hydrogen atom is explained using wave mechanics
to describe atomic orbitals.
Uses of Planck quantum theory in Bohr Model
Bohr’s starting point was to realize that classical
mechanics by itself could never explain the atom’s
stability. A stable atom has a certain size so that any
equation describing it must contain some fundamental
constant or combination of constants with a dimension
of length. The classical fundamental constants—
namely, the charges and the masses of the electron and
the nucleus cannot be combined to make a length.
Bohr noticed, however, that the quantum constant
formulated by German physicist Max Planck has
dimensions which, when combined with the mass
and charge of the electron, produce a measure of
length. Numerically, the measure is close to the known
size of atoms. This encouraged Bohr to use Planck’s
constant in searching for a theory of the atom.
Planck constant and Bohr Model
Planck had introduced his constant in 1900 in a formula explaining
the light radiation emitted from heated bodies. According to
classical theory, comparable amounts of light energy should be
produced at all frequencies. This is not only contrary to observation
but also implies the absurd result that the total energy radiated by a
heated body should be infinite. Planck postulated that energy can
only be emitted or absorbed in discrete amounts, which he
called quanta (Latin for “how much”). The energy quantum is related
to the frequency of the light by a new fundamental constant, h.
When a body is heated, its radiant energy in a particular frequency
range is, according to classical theory, proportional to
the temperature of the body. With Planck’s hypothesis, however, the
radiation can be emitted only in quantum amounts of energy. If the
radiant energy is less than the quantum of energy, the amount of
light in that frequency range will be reduced. Planck’s formula
correctly describes radiation from heated bodies. Planck’s constant
has the dimensions of action, which may be expressed as units of
energy multiplied by time, units of momentum multiplied by length,
or units of angular momentum. For example, Planck’s constant can
be written as h = 6.6 × 10−34 joule∙seconds.
Overview of
Principal Quantum Number
As n increases, the electron is also at a higher orbit and is,
therefore, less tightly bound to the nucleus. For higher n the
electron is farther from the nucleus, on average. For each
value of n there are n accepted ℓ (azimuthal) values ranging
from 0 to n − 1 inclusively, hence higher-n electron states
are more numerous. Accounting for two states of spin,
each n-shell can accommodate up to 2n2 electrons.
In a simplistic one-electron model described below, the total
energy of an electron is a negative inverse quadratic function
of the principal quantum number n, leading to degenerate
energy levels for each n > 1. In more complex systems—
those having forces other than the nucleus–electron Coulomb
force—these levels split. For multielectron atoms this
splitting results in "subshells" parametrized by ℓ. Description
of energy levels based on n alone gradually becomes
inadequate for atomic numbers starting from 5 (boron) and
fails completely on potassium (Z = 19) and afterwards.
History of principal quantum number
The principal quantum number was first
created for use in the semiclassical Bohr
model of the atom distinguishing between
different energy levels. With the development
of modern quantum mechanics, the simple
Bohr model was replaced with a more
complex theory of atomic orbitals. However,
the modern theory still requires the principal
quantum number.
Definition
The principal quantum number is the quantum
number denoted by n and which indirectly describes the
size of the electron orbital. It is always assigned an
integer value (e.g., n = 1, 2, 3...), but its value may never
be 0. An orbital for which n = 2 is larger, for example,
than an orbital for which n = 1. Energy must be absorbed
in order for an electron to be excited from an orbital near
the nucleus (n = 1) to get to an orbital further from the
nucleus (n = 2).
The principal quantum number is cited first in the set of
four quantum numbers associated with an electron.
The principal quantum number has the greatest effect on
the energy of the electron. It was first designed to
distinguish between different energy levels in the Bohr
model of the atom but remains applicable to the modern
atomic orbital theory.
Derivation
There is a set of quantum numbers associated with the energy
states of the atom. The four quantum numbers n, ℓ, m,
and s specify the complete and unique quantum state of a single
electron in an atom, called its wave function or orbital. Two
electrons belonging to the same atom cannot have the same
values for all four quantum numbers, due to the Pauli exclusion
principle. The Schrödinger wave equation reduces to the three
equations that when solved lead to the first three quantum
numbers. Therefore, the equations for the first three quantum
numbers are all interrelated. The principal quantum number
arose in the solution of the radial part of the wave equation as
shown below.
The Schrödinger wave equation describes
energy eigenstates with corresponding real numbers En and a
definite total energy, the value of En. The bound state energies
of the electron in the hydrogen atom are given by:
Derivation
The parameter n can take only positive
integer values. The concept of energy levels
and notation were taken from the
earlier Bohr model of the atom.
Schrödinger's equation developed the idea
from a flat two-dimensional Bohr atom to
the three-dimensional wavefunction model.
In the Bohr model, the allowed orbits were
derived from quantized (discrete) values of
orbital angular momentum, L according to
the equation
Explanation
where n = 1, 2, 3, … and is called the principal quantum number,
and h is Planck's constant. This formula is not correct in quantum
mechanics as the angular momentum magnitude is described by
the azimuthal quantum number, but the energy levels are
accurate and classically they correspond to the sum
of potential and kinetic energy of the electron.
The principal quantum number n represents the relative overall
energy of each orbital. The energy level of each orbital increases
as its distance from the nucleus increases. The sets of orbitals
with the same n value are often referred to as an electron shell.
The minimum energy exchanged during any wave–matter
interaction is the product of the wave frequency multiplied
by Planck's constant. This causes the wave to display particle-like
packets of energy called quanta. The difference between energy
levels that have different n determine the emission spectrum of
the element.
In the notation of the periodic table, the main shells of electrons
are labeled:
K (n = 1), L (n = 2), M (n = 3), etc.
Overview of Planck postulates
One phenomenon that seemed to contradict
the theories of classical physics was blackbody
radiation, which is electromagnetic radiation
given off by a hot object. The wavelength (i.e.
color) of radiant energy emitted by a blackbody
depends on only its temperature, not its
surface or composition. Hence an electric stove
burner or the filament of a space heater glows
dull red or orange when heated, whereas the
much hotter tungsten wire in an incandescent
light bulb gives off a yellowish light.
Blackbody Radiation
A B
Explanation of figure A
When heated, all objects emit electromagnetic
radiation whose wavelength (and color)
depends on the temperature of the object. A
relatively low-temperature object, such as a
horseshoe forged by a blacksmith, appears
red, whereas a higher-temperature object,
such as the surface of the sun, appears
yellow or white.
Explanation of figure B
Relationship between the Temperature of an Object and the
Spectrum of Blackbody Radiation it Emits. At relatively low
temperatures, most radiation is emitted at wavelengths
longer than 700 nm, which is in the infrared portion of the
spectrum. The dull red glow of the electric stove element in
Figure B is due to the small amount of radiation emitted at
wavelengths less than 700 nm, which the eye can detect. As
the temperature of the object increases, the maximum
intensity shifts to shorter wavelengths, successively resulting
in orange, yellow, and finally white light. At high
temperatures, all wavelengths of visible light are emitted with
approximately equal intensities. The white light spectrum
shown for an object at 6000 K closely approximates the
spectrum of light emitted by the sun (Figure B. Note the sharp
decrease in the intensity of radiation emitted at wavelengths
below 400 nm, which constituted the ultraviolet catastrophe.
The classical prediction fails to fit the experimental curves
entirely and does not have a maximum intensity.
Planck postulate
The Planck postulate (or Planck's postulate),
one of the fundamental principles
of quantum mechanics, is the postulate that
the energy of oscillators in a black body is
quantized, which states that electromagnetic
radiation from heated bodies is not emitted
as a continuous flow but is made up of
discrete units or quanta of energy, the size of
which involve a fundamental physical
constant (Planck's constant) and is given by
Planck postulate
Where n is an integer(1,2,3.......) and h is planck
constant and v (the Greek letter nu, not the Latin
letter v) is the frequency of the oscillator.
The postulate was introduced by Max Planck in
his derivation of his law of black body
radiation in 1900. This assumption allowed
Planck to derive a formula for the
entire spectrum of the radiation emitted by a
black body. Planck was unable to justify this
assumption based on classical physics; he
considered quantization as being purely a
mathematical trick, rather than (as is now
known) a fundamental change in the
understanding of the world. In other words,
Planck then contemplated virtual oscillators.
Planck curve
Einstein and Planck theory
In 1905, Albert Einstein adapted the Planck
postulate to explain the photoelectric effect,
but Einstein proposed that the energy of
photons themselves was quantized, and that
quantization was not merely a feature of
microscopic oscillators. Planck's postulate was
further applied to understanding the Compton
effect, and was applied by Niels Bohr to
explain the emission spectrum of
the hydrogen atom and derive the correct
value of the Rydberg constant.
