B. Sc.

I sem
(CBCS)

Atomic Structure

Dr. Divya Hegde

Dept. of Chemistry
M. M. Arts and Science College, Sirsi
 Contents
• Review of Bohr’s theory and its limitations,
• Dual behavior of matter and radiation,
• De-Broglie relation. Heisenberg Uncertainty principle.
• Hydrogen atom spectra. Need of a new approach to Atomic structure.
• What is quantum mechanics? Time independent .
• Schrodinger equation and meaning of various terms in it.
• Significance of ѱ and ѱ2, Schrodinger equation for hydrogen atom.
• Radial and angular parts of the hydogenic wave functions (atomic orbitals) and their
variations for 1s, 2s, 2p, 3s, 3p and 3d orbitals (graphical representation).
• Radial and angular nodes and their significance.
• Radial distribution functions and the concept of the most probable distance with special
reference to 1s and 2s atomic orbitals.
• Significance of Quantum Numbers, orbital angular momentum and quantum numbers ml and
ms.
• Shapes of s. p and d atomic orbitals, nodal planes.
• Discovery of spin, spin quantum number (s) and magnetic spin quantum number (ms).
• Rules for filling electrons in various orbitals, Electronic configuration of atoms.
• Stability of half filled and completely filled orbitals, concept of exchange energy.
• Relative energies of atomic orbitals, Anamolous electronic configurations.
 Introduction

• To understand the behavior of molecules and solids we need to understand

atoms.
• John Dalton (1809) regarded the atom as a hard, dense and smallest individual
particle of matter.
• However the emission of negatively and positively charged particles from
radioactive elements as well as from gases on the passage of electricity at very
low pressures, convinced the scientists that atom is not indivisible but consists
of smaller fundamental particles.
• It is now fully established that atom consists of 3 major fundamental particles
called electrons, protons and neutrons.
 Review of Bohr’s theory
• Neils Bohr in 1913 put forward his theory of atoms. He
agreed that atom consists of very small nucleus at the centre
containing all the protons and neutrons. And electrons
revolve around the nucleus.
• Main postulates of his theory are-
1) The electrons in an atom revolve round the nucleus only in certain selected
orbits. These circular orbits are called as “stationary states”. These energy
levels are also designated as K, L, M, N etc. The farther the energy level from
the nucleus, greater is the energy associated with it.
2) As long as the electron revolves in the same orbit, it does not lose or gain the
energy i.e., energy remains constant.
3) The energy of the electrons can’t change continuously. Energy changes only
when electron jumps from one energy level to another. Electrons gains energy
and jumps from one energy level to another. Electrons gains energy and
jumps to higher energy level and it loses energy when it jumps from higher
energy level to lower energy level.
4) The change in energy when electron jumps from one orbit to another orbit is
given as-
∆E =E2-E1 = hν
where ‘h’ is Plank’s constant and ‘ν’ is frequency of radiation.

5) The angular momentum of an electron moving round the nucleus is

quantized. The angular momentum is given by ‘mvr’, where ‘m’ is mass of
the electron, ‘v’ is velocity of the electron and ‘r’ is radius of the orbit. The
angular momentum is given as-

where ‘n’ is any integer, 1,2,3,….

It is called quantization of angular momentum.
Explanation of H-spectrum on the basis of Bohr’s theory:

The H-atom contains only one electron. But its spectrum consists of a large number of
lines.

Suppose energy is supplied to this sample (of the gas) different atoms will absorb
different amounts of energy. The solitary electron (present in the first energy level) in
different atoms of hydrogen gets excited, i.e., the electron shifts from the energy level 1
(lowest energy level/ground state) to different higher energy levels 2,3,4 etc depending
on the amount of energy abrosrbed by the atoms of hydrogen. The excited state of an
electron is short lived; therefore the excited electrons are forced to return to lower energy
levels. Thus a large number of transitions in each transitions energy is released which
appears in the form of radiation of specific frequency and hence of specific wavelength.
The resulting spectrum of hydrogen consists of a large number of sharp lines
which spread over UV, visible and IR regions of electromagnetic spectrum.
A schematic of the hydrogen spectrum shows several series named for those who contributed most
to their determination. Part of the Balmer series is in the visible spectrum, while the Lyman series is
entirely in the UV, and the Paschen series and others are in the IR. Values of nf and ni are shown for
some of the lines.
 Electronic transitions corresponding to the spectral series of hydrogen

It is found that, the wave number, ῡ of any spectral line in any series can be calculated
using Rydberg formula, i.e.,

(n2>n1), (ῡ=l/λ), (ῡ= ν/c)

C= velocity of light = 3×108m/s.
Where R is a constant called Rydberg constant and its value is 109.686×105m-1
• For a particular series n1 is constant, while n2 varies from one line to another.

Series Value of n1 Value of n2 Region of

spectra
Lyman 1 2,3,4,5,6,7…. UV

Balmer 2 3,4,5,6,7…. Visible

Paschen 3 4,5,6,7… IR

Brackett 4 5,6,7…. IR

Pfund 5 6,7,… IR
Merits of Bohr Theory:
• Bohr’s theory explains the formation of lines in the emission
spectrum of hydrogen.
• The theory clearly explains the stability of the atom.
• The radii of hydrogen and hydrogen like particles which contain a
single electron are determined experimentally are in good agreement
with the calculated using Bohr’s theory.
• The wave numbers of the spectral lines as calculated from the
Bohr’s theory are in good agreement with experimental values.
• The values of the Rydberg constant calculated using the Bohr’s
theory is very close to the experimental value.
Limitations of Bohr’s atomic model:
• Bohr’s model is unable to explain the spectra and energy of atoms containing more
than one electron.

• Bohr’s theory predicts the origin of only one spectral line from an electron between
any two energy level but fails to explain the multiple or fine spectrum of atoms. The
fine spectrum of atom contains many more closely spaced lines than predicted by
Bohr’s model.

• This model is unable to explain the effect of electric and magnetic fields on the
spectra of atoms. When a magnetic field is applied on an atoms it’s usually
observed spectral lines gets split. This effect is known as Zeeman effect. Spectral
lines also get split in the presence of an electric field. This effect is known as Stark
effect. Both these effects can’t be explained on the basis of Bohr’s model.
• Bohr’s assumptions that electrons revolve in orbits without emission or absorption

of energy and the condition of quantization of angular momentum has no

theoretical basis.

• In 1923, De-Broglie suggested that electron like light has a dual character. It has

particle as well as wave character. Bohr treated the electron only as a particle.

• Another objection to Bohr’s theory came from Heisenberge’s uncertainty principle.

According to this principle it is impossible to determine simultaneously the exact

position and momentum of small moving particle like an electron. According to

Bohr’ theory an electron follows a fixed circular path with definite energy and thus

both its position and direction can be well defined. However these principles stated

that the path of the electron is not definite. It is of probable nature. Thus

uncertainity principle goes against Bohr’s theory.

Dual behavior of matter and radiation

• Dual Nature of Matter and Radiation means the duality in the nature of
matter, namely particle nature and a wave nature.
• Various experiments by various scientists were done to prove it. For
example, light behaves both as a wave and as a particle.
• If you are observing phenomenon like the interference, diffraction or
reflection, you will find that light behaves as a wave.
• However, if you are looking at phenomena like the photoelectric effect, you
will find that light behaves as a particle.
De-Broglie’s hypothesis:

• According to De-Broglie’s theory electron

has a dual character, both as a material particle and as a wave.

He derived an expression for calculating the wavelength λ associated with the

motion of a particle of mass ‘m’ moving with velocity ‘v’ according to which,
λ= h/mv, where ‘h’ is Plank’s constant.
Davisson and Germer experimentally demonstrated the wave nature of
the electrons by subjecting them to diffraction. These studies confirmed De-
Broglie idea of matter waves.
De-Broglie’s equation:

Derivation- According to Einsteins mass energy relation the energy associated by a photon is-
E=mc2 ---- (1)
where, m is mass and c is the velocity of light (3×108ms-1).
According to Plank’s equation
E=h ν ---- (2)
where h is Plank’s constant and ν is frequency of radiation.
Equating equation (1) and (2), we get,
mc2 =h ν
mc2 =h c/λ (⸪ ν=c/λ)
λ = hc/mc2
λ = h/mc ---- (3)
Replacing c by v in equation (3), we get
λ = h/mv ---- (4)
Equation (4) is the De-Broglie’s equation, where v is velocity of electron.
Since ‘mv’ represents momentum, the De-Broglie’s equation can also be written as
λ = h/p
Heisenberg’s Uncertainty Principle:

CHEMISTRY
 Heisenberg’s Uncertainty Principle:
“It is impossible to measure or determine simultaneously
the exact position and the exact momentum or velocity of a
subatomic particle like electron”. If ∆x represents the error or
uncertainty in the measurement of position and ∆P represents the
uncertainty in the measurement of momentum of a subatomic
particle like electron, then according to this principle both ∆x
and ∆P may be related as-

∆x. ∆P ≥ h/4π
 What is quantum mechanics?

• Quantum mechanics is the study of the motion of objects that are

atomic or subatomic in size and thus demonstrate wave-particle
duality.

• In classical mechanics, the size and mass of the objects involved

effectively obscures any quantum effects so that such objects appear
to gain or lose energies in any amounts.

• Particles whose motion is described by quantum mechanics gain or

lose energy in the small pieces called quanta.

• One of the fundamental (and hardest to understand) principles of

quantum mechanics is that the electron is both a particle and a
wave.
• In the everyday macroscopic world of things we can see,
something cannot be both. But this duality can exist in the
quantum world of the submicroscopic at the atomic scale.

• At the heart of quantum mechanics is the idea that we cannot

specify accurately the location of an electron.

• All we can say is that there is a probability that it exists

within this certain volume of space. The scientist Erwin
Schrödinger developed an equation that deals with these
calculations, which we will not pursue at this time.
the electron orbitals presented here represent a volume of space within which an electron
would have a certain probability. For example, in a simple lowest-energy state hydrogen
atom, the electrons are most likely to be found within a sphere around the nucleus of an
atom. In a higher energy state, the shapes become lobes and rings. With the exception of
the n = 1 orbital, all orbitals in the top row are cutaway to show the concentric spheres.
 Important Features of the Quantum Mechanical Model of Atom

1. The energy of electrons in atoms is quantized (i.e., can only have certain specific
values), for example when electrons are bound to the nucleus in atoms.
2. The existence of quantized electronic energy levels is a direct result of the wave like
properties of electrons and are allowed solutions of Schrödinger wave equation.
3. Both the exact position and exact velocity of an electron in an atom cannot be
determined simultaneously (Heisenberg uncertainty principle). The path of an electron
in an atom therefore, can never be determined or known accurately. That is why, one
talks of only probability of finding the electron at different points in an atom.
4. An atomic orbital is the wave function for an electron in an atom. Whenever an
electron is described by a wave function, we say that the electron occupies that orbital.
Since many such wave functions are possible for an electron, there are many atomic
orbitals in an atom. These “one electron orbital wave functions” or orbitals form the
basis of the electronic structure of atoms. In each orbital, the electron has a definite
energy. An orbital cannot contain more than two electrons. In a multi-electron atom, the
electrons are filled in various orbitals in the order of increasing energy. For each
electron of a multi-electron atom, there shall, therefore, be an orbital wave function
characteristic of the orbital it occupies. All the information about the electron in an
atom is stored in its orbital wave function and quantum mechanics makes it possible to
extract this information.
 Time independent Schrödinger wave equation
• The time-dependent Schrödinger equation predicts that wave functions can
form standing waves, called stationary states. These states are particularly
important as their individual study later simplifies the task of solving the
time-dependent Schrödinger equation for any state. Stationary states can
also be described by a simpler form of the Schrödinger equation, the time-
independent Schrödinger equation (TISE).

where E is a constant equal to the energy level of the system. This is only used
when the Hamiltonian itself is not dependent on time explicitly. However, even
in this case the total wave function still has a time dependency.
In the language of linear algebra, this equation is an eigenvalue equation.
Therefore, the wave function is an eigen function of the Hamiltonian operator
with corresponding eigenvalue(s) E.
 Time-independent Schrödinger equation
(single nonrelativistic particle)

Here, the form of the Hamiltonian operator comes from classical mechanics,
where the Hamiltonian function is the sum

That is,

for a single particle in the non-relativistic limit of the kinetic and potential
energies.
Time-independent Schrödinger equation
 Schrödinger wave equation for Hydrogen atom:

• If the electrons behave as a wave, there must be a wave equation to

describe their behavior.

• Erwin Schrödinger, in 1926, gave a wave equation to describe the wave

behavior of electrons in atoms and molecules.

• In Schrödinger wave model of an atom, the discrete energy levels or orbits

proposed by Bohr are replaced by mathematical functions ѱ which are
related with the probability of finding electrons at various places around the
nucleus.
The Schrodinger wave equation for an electron wave
propagating in three dimensions in space is written as follows:
 Eigen wave function and Eigen value:

• Schrodinger wave equation is a second order differential and so it has many

solutions, when we solve Schrodinger wave equation for ѱ, we get many
values of ѱ. Some of these values are imaginary, while others are real
values.

• The imaginary values of ѱ cannot be accepted.

• Only those values of ѱ which gives definite and acceptable values of the
wave function ѱ are called as ‘ Eigen wave functions’.

• The value of E given by a particular wave function ia called ‘Eigen value’.

 Characteristics of an Eigen wave function:

• The function must be finite.

• It should be single. It shouldn’t have more than one value at a

point in space.

• It should be continuous.

• The function must be normalized i.e., it should obey

2 , where dr is small volume element and ѱ2 is
probability of finding the electron in a small colume element
dr.
 Significance of ѱ and ѱ2:

• The wave function ѱ by itself has no significane. Since it can’t

represent the probability of finding the electron in a small
value round the nucleus. Because it can have both positive and
negative value.
• But probability of finding the electron can be zero or positive,
but can’t be negative.
• The square of ѱ i.e., ѱ2 is always positive and hence measures
the probability of finding the electron.
 Probability density:
• According to Heisenberg’s uncertainty principle, we can never know the
exact position of the electron moving around the nucleus with a particular
velocity.
• Therefore, we talk in terms of the probability of its location in any given
region.
• In other words, we define its position by a probability function.
• Such a probability function will vary with the position of the region in
space in which we want to find the probability of the existence of the
electron.
• The small volume element dxdydz around the point x, y, z is also written as
τ. The function ρ is also known as probability density.
• In Bohr theory the electrons were considered as particles revolving round
the nucleus in circular orbits whereas this theory visualizes an electron in
terms of probability and is unable to define an exact path for it. The space
around the nucleus of the atom in which there is maximum probability of
finding the electron is called an orbital.
 Radial Probability Distribution Curve
• Schrodinger wave equation may be separated into a product of three
functions, one dependent on r, the second dependent on θ and the third
dependent on ϕ. Thus, Ѱ (r, θ, ϕ) = R(r) (θ) ɸ (ϕ)
• The probability of finding an electron in a spherical shell of thickness dr at
various distances r from the nucleus can be measured from the radial
distribution factor, R(r) by plotting (product of surface area 4πr2 and the
square of the radial function) 4πr2R2 (r) dr v/s r. Plots of this function for
the hydrogen 1s, 2s, 2p, 3s, 3p and 3d orbitals v/s r are given in below
figure.

It can be seen that the

number of peaks in the
plots for the s orbital is
equal to the n value, i.e.,
1 for 1s, 2 for 2s and 3 for
3s. In plots for p and d
orbitals, the number of
peaks are (n-1) and (n-2)
respectively,

Radial distribution of probability of finding the electron for different states of the hydrogen atom.
 Angular Probability Distribution Curves
• The total angular function (θ) ɸ (ϕ) depends only on the direction and
remains independent of the distance from the nucleus.
• The angular probability distribution curves for s and p orbitals are shown in
below figure.
• The diagrams are such that if a straight line is drawn at a certain angle
from the origin O to cut the surface at a point P, the length of the line
proportional o the probability of finding the electron anywhere in that
direction.

Angular probability distribution curves for s and p-electrons

• The diagram for an s orbital is a spherical surface, so that the length of the
line OP is the same in all directions.
• This means there are equal chances of finding an s electron in any direction
from the nucleus.
• This is what is implied when we say that s orbitals are spherically
symmetrical.
• The three p-orbitals have definite directional properties and are mutually
inclined in which the electron will be found is along the x-axis.
• The probability decreases rapidly as the angle between the line OP and x-
axis increases. Similarly we can describe py and pz orbitals.
Radial distribution functions
 Orbital Nodes
• Nodes are the points in space around a nucleus where the probability of
finding an electron is zero. However, there are two kinds of nodes, radial
nodes and angular nodes.
2p orbitals have a single angular node, a plane, separating the positive and
negative phases of the orbitals. This is shown below in gray.
All the 3d orbitals have two angular nodes. In four of the orbitals, these nodes
are planes separating the positive and negative phases of the orbitals. In the
fifth orbital, the nodes are two conical surfaces.

y2
Radial nodes are nodes inside the orbital lobes as far as I can
understand. Its easiest to understand by looking at the s-orbitals,
which can only have radial nodes.
• To see what an angular node is, then, let's examine the 2p-
orbital - an orbital that has one node, and that node is angular.
• Nodes are points of zero electron density. From the principal quantum
number n and the azimuthal quantum number ℓ, you can derive the number
of nodes, and how many of them are radial and angular.
number of nodes = n−1
angular nodes = ℓ
radial nodes = (number of nodes) − (angular nodes)
So each type of orbital (s,p,d etc) has its own unique, fixed number of angular
nodes, and then as n increases, you add radial nodes.
• Ex:
• For the second shell, n=2, which yields 1 node.
• For the 2s orbital, ℓ=0, which means the node will be radial
• For the 2p orbital, ℓ=1, which means the node will be angular
 Radial and angular nodes and their significance

• Radial wave functions for a given atom depend only upon the
distance, r from the nucleus.

• Angular wave functions depend only upon direction and in

effect, describe the shape of an orbital.