Course Name : Condensed Matter Physics

Course code: SPHA5301

Batch : II M.Sc., Physics (2019-2021)
UNIT IV
ATOMIC MOLECULAR STRUCTURE

Condensed Matter Physics (SPHA5301) 1

 Contents
• Central field approximation

• Thomas Fermi model and its application

• Hartree and Hartree Fock equations

• hydrogen molecule

• Heiyrt (Heitler) London model

• LCAO

• Hybridization.
In materials physics, the central field
approximation for many-electron atoms takes the
combined electric fields of the nucleus and all the 
electrons acting on any of the electrons to be radial and
to be the same for all the electrons in the atom.

That is, every electron sees an identical potential   that

is only a function of its distance from the nucleus.

This facilitates an approximate analytical solution to the 

eigenvalue problem for the Hamiltonian operator.
SCF cycle (Ex.)
 Hartree-Fock Equations
(Solved by the Self-Consistent Field Method)
• The Hartree method is used to approximate the wavefunction and the
energy of a quantum multi-electron system in a stationary state.

• This approximation assumes that the exact N-body wave function of the

system can be approximated by a product of single-electron
wavefucntions. 

• In principle, the Hartree-Fock technique enables us to calculate all the

states and their energies for any atom in the periodic table.

• However, the computational effort required increases rapidly with the

number of electrons since the size of the Slater determinant scales with
the square of the number of single-electron states involved.
• The generic multielectron atom including terms for the additional
electrons with a general charge Z; e.g.

|r−R| is the distance between the electron and the nucleus, The Hamiltonian
must also have terms for electron-electron repulsion (also in atomic units)

|r−r′| is the distance between electron 1 and electron 2. So the proper multi-
electron Hamiltonian can be constructed
• It is helps to predict that exact solutions to the multi-electron Schrödinger
equation would consist of a family of multi-electron wavefunctions, each with
an associated energy eigenvalue.

• These wavefunctions and energies would describe the ground and excited
states of the multi-electron atom, just as the hydrogen wavefunctions and
their associated energies describe the ground and excited states of the
hydrogen atom. We would predict quantum numbers to be involved, as well.

• The fact that electrons interact through their electron-electron repulsion

means that an exact wavefunction for a multi-electron system would be a
single function that depends simultaneously upon the coordinates of all the
electrons; i.e., a multi-electron wavefunction:
• |ψ(r1,r2,⋯ri)⟩

• Unfortunately, the electron-electron repulsion terms make it impossible to

find an exact solution to the Schrödinger equation for many-electron atoms.
 The Hartree Approximation

• For the Schrödinger equation to be analytically solvable, the variables

must be separable - the variables are the coordinates of the electrons.

• To separate the variables in a way that retains information about

electron-electron interactions, the electron-electron term must be
approximated so it depends only on the coordinates of one electron.

• Such an approximate Hamiltonian can account for the interaction of

the electrons in an average way.

• The exact one-electron eigenfunctions of this approximate

Hamiltonian then can be found by solving the Schrödinger equation.

• These functions are the best possible one-electron functions.

• The Hartree approximation starts by invoking an initial  that the multi-electron
wavefunction  can be expanded as a product of single-electron wavefunctions (i.e., orbitals)

• |ψ(r1,r2,…,rN) ⟩ ≈ ψ1(r1)ψ2(r2)…
• from which it follows that the electrons are independent, and interact only via the mean-
field Coulomb potential. This yields one-electron Schrödinger equations of the form

• Or

• where V(r) is the potential in which the electron moves; this includes both the nuclear-
electron interaction.
• We smear the other electrons out into a smooth negative
charge density ρ(r′) leading to a potential of the form.

• The sum over runs over all occupied states; i.e., only the states of electrons that
exist in the atom.
• The wavefunctions that from this approach with the
Hamiltonian He(r)He(r) involve possess three kinds of energies (mentioned above)
What is meant by LCAO
(Linear Combination of Atomic orbitals)?

The Linear combination of atomic orbitals which is also known as LCAO is an approximate method for representing molecular orbitals. It’s more of a superimposition method where
constructive interference of two atomic wave function produces a bonding molecular orbital whereas destructive interference produces non-bonding molecular orbital.
• Conditions to be satisfied:
The conditions that are required for a linear combination
of atomic orbitals are as follows:
•
Same Energy of combining orbitals – 
• The combining atomic orbitals must have same or nearly
same energy. This means that 2p orbital of an atom can
combine with another 2p orbital of another atom but 1s
and 2p cannot combine as they have appreciable energy
difference.
• Same symmetry about the molecular axis – 
• combining atoms should have same symmetry around the molecular axis for
proper combination, otherwise, the electron density will be sparse.
For e.g. all the sub-orbitals of 2p have same energy but still, the 2pz orbital of an
atom can only combine with a 2pz orbital of another atom but cannot combine
with 2px and 2py orbital as they have a different axis of symmetry. In general, the
z-axis is considered as the molecular axis of symmetry

• Proper Overlap between the atomic orbitals – The two atomic orbitals will
combine to form molecular orbital if the overlap is proper. Greater the extent of
overlap of orbitals, greater will be the nuclear density between the nuclei of the
two atoms.

• The condition can be understood by two simple requirements. For the formation
of proper molecular orbital, proper energy and orientation are required. For
proper energy, the two atomic orbitals should have the same energy of orbitals
 and for the proper orientation, the atomic orbitals should have proper overlap
and the same molecular axis of symmetry.
• Covalent bonds and linear combination of
atomic orbitals

• Consider two atoms next to each other.

• Since different orbitals of an atom are
separated in energy, we consider one orbital
per atom

• That the atoms are sufficiently far apart, so

that the shape of the orbitals or the energy of
the orbitals doesn't change much.
• Summary
• Electrons in atoms occupy shells, with only the
outermost shell contributing to interatomic
interaction.
• The LCAO method reduces the full Hamiltonian to
a finite size problem written in the basis of
individual orbitals.
• If two atoms have one orbital and one atom each,
electron movement makes the atoms attract.
 HYBRIDIZATION
• Hybridization is defined as the concept of mixing two atomic orbitals with the
same energy levels to give a degenerated new type of orbitals. This
intermixing is based on quantum mechanics. The atomic orbitals of the same
energy level can only take part in hybridization and both full filled and half-
filled orbitals can also take part in this process, provided they have equal
energy.

• During the process of hybridization, the atomic orbitals of similar energy are
mixed together such as the mixing of two ‘s’ orbitals or two ‘p’ orbital’s or
mixing of an ‘s’ orbital with a ‘d’ orbital.

• What are hybrid orbitals?

• The hybrid orbitals can be defined as the combination of standard atomic
orbitals resulting in the formation of new atomic orbitals.
• a ‘p’ orbital or ‘s’ orbital with a ‘d’ orbital.
 Types of Hybridization

• Based on the types of orbitals involved in mixing, the hybridization can be

classified as sp3, sp2, sp, sp3d, sp3d2, sp3d3. Let us now discuss the various
types of hybridization, along with their examples.

1) sp Hybridization
• sp hybridization is observed when one s and one p orbital in the same main shell
of an atom mix to form two new equivalent orbitals. The new orbitals formed
are called sp hybridized orbitals. It forms linear molecules with an angle of 180°
• This type of hybridization involves the mixing of one ‘s’ orbital and one ‘p’ orbital
of equal energy to give a new hybrid orbital known as an sp hybridized orbital.
• sp hybridization is also called diagonal hybridization.
• Each sp hybridized orbital has an equal amount of s and p character, i.e., 50% s
and p character.
Examples of sp Hybridization:
All compounds of beryllium like BeF2, BeH2, BeCl2

All compounds of carbon-containing triple Bond like C2H2.

• sp2 Hybridization

• sp2 hybridisation is observed when one s and two p orbitals of the same

shell of an atom mix to form 3 equivalent orbital. The new orbitals
formed are called sp2 hybrid orbitals. 
• sp2 hybridization is also called trigonal hybridization.
• It involves mixing of one ‘s’ orbital and two ‘p’ orbital’s of equal energy
to give a new hybrid orbital known as sp2.
• A mixture of s and p orbital formed in trigonal symmetry and is
maintained at 1200.
• All the three hybrid orbitals remain in one plane and make an angle of
120° with one another. Each of the hybrid orbitals formed has 33.33% s
character and 66.66% ‘p’ character.
• The molecules in which the central atom is linked to 3 atoms and is sp2
hybridized have a triangular planar shape.
Examples of sp2 Hybridization
All the compounds of Boron i.e. BF3, BH3
All the compounds of carbon containing a carbon-carbon double bond,
Ethylene (C2H4)
• sp3 Hybridization
• When one ‘s’ orbital and 3 ‘p’ orbitals belonging to the same
shell of an atom mix together to form four new equivalent
orbital, the type of hybridization is called a tetrahedral
hybridization or sp3. The new orbitals formed are
called sp3 hybrid orbitals.
• These are directed towards the four corners of a regular 
tetrahedron and make an angle of 109°28’ with one
another.
•  The angle between the sp3 hybrid orbitals is 109.280
• Each sp3 hybrid orbital has 25% s character and 75% p
character.
• Example of sp3 hybridization: ethane (C2H6), methane.
Video
• Hydrogen molecule (in text)
 Heitler and London Theory
•Valence Bond Theory (Heiyrt)

•Heitler and London introduced this theory. This is primarily based on the concepts of 
atomic orbitals, electronic configuration of elements, the overlapping of atomic
orbitals, hybridization of atomic orbitals.

• The overlapping of atomic orbitals results in the formation of a chemical bond. The
electrons are localized in the bond region due to overlapping.

•Valence bond theory describes the electronic structure of molecules.

•The theory says that electrons fill the atomic orbitals of an atom within a molecule.

• It also states that the nucleus of one atom is attracted to the electrons of another
atom.
 Definition
• It is a theory which describes chemical bonding.

• VBT states that the overlap of incompletely filled

atomic orbitals leads to the formation of a
chemical bond between two atoms.

• The unpaired electrons are shared and a hybrid

orbital is formed.
• Postulates of Valence Bond Theory

• The overlapping of two half-filled valence orbitals of two different atoms results in the formation of the
covalent bond.

• The overlapping causes the electron density between two bonded atoms to increase. This gives the
property of stability to the molecule.

• In case the atomic orbitals possess more than one unpaired electron, more than one bond can be
formed and electrons paired in the valence shell cannot take part in such a bond formation.

• Covalent bonds are formed when two valence orbitals (half-filled) belonging to two different atoms
overlap on each other. The electron density in the area between the two bonding atoms increases as a
result of this overlapping, thereby increasing the stability of the resulting molecule.

• The presence of many unpaired electrons in the valence shell of an atom enables it to form multiple
bonds with other atoms. The paired electrons present in the valence shell do not take participate in the
formation of chemical bonds as per the valence bond theory.

• A covalent bond is directional. Such a bond is also parallel to the region of overlapping atomic orbitals.

• Based on the pattern of overlapping, there are two types of covalent bonds: sigma bond and a pi bond.
The covalent bond formed by sidewise overlapping of atomic orbitals is known as pi bond whereas the
bond formed by overlapping of atomic orbital along the inter nucleus axis is known as a sigma bond.
• Based on the overlapping of orbitals, how many types of covalent
bonds are formed and what are they?
• Answer: Based on the overlapping of orbitals, two types of covalent
bonds are formed. These are known as sigma(σ) and pi(π) bonds.
• Sigma bonds are formed by the end-to-end overlap of atomic
orbitals along the inter-nuclear axis known as a head-on or axial
overlap. End-on overlapping is of three types, they are s-s
overlapping, s-p overlapping and p-p overlapping.
• A pi bond is formed when atomic orbitals overlap in a specific way
that their axes remain parallel to each other and perpendicular to
the internuclear axis.
• Applications of Valence Bond Theory

• The maximum overlap condition which is described by the valence bond

theory can explain the formation of covalent bonds in several molecules.

• This is one of its most important applications. For example, the difference
in the length and strength of the chemical bonds in H 2 and F2 molecules
can be explained by the difference in the overlapping orbitals in these
molecules.

• The covalent bond in an HF molecule is formed from the overlap of the 1s

orbital of the hydrogen atom and a 2p orbital belonging to the fluorine
atom, which is explained by the valence bond theory.
• Limitations of Valence Bond Theory

• It fails to explain the tetravalency of carbon.

• No insight offered on the energies of the electrons.
• The theory assumes that electrons are localized in
specific areas.
• It does not give a quantitative interpretation of the
thermodynamic or kinetic stabilities of coordination
compounds.
• No distinction between weak and strong ligands.
Electronic configuration

1s2 2s2 2p6 3s2 3p6 4s2 3d10

4p6 5s2 4d10 5p6 6s2 4f14 5d10
6p6 7s2 ------

5 f14 6d10 7p 6 8s2 6f 14 7d 10 8p

6
9s 2 …….

No of electron in an orbital
2(2ℓ+1).
S-2; p-6; d-10; f-14

No of electrons in a Shell - 2(n2)

electrons.
 Atomic number
Neon - 10
Aluminium – 13
Argon - 18
Calcium - 20
Fe -26
• Thomas Fermi model in text