T O O L S OF C OM P U T A T IO N AL

CHEMISTRY

Lecture 9-10

“Computational Chemistry: Introduction to the Theory and Applications of Molecular and

Quantum Mechanics”, Errol Lewars, Kluwer Academic Publishers, 2004.
 Some definitions
❖ A wave function (denoted as ψ (psi) in quantum mechanics
describes the quantum state of a set of particles in an isolated
system.“ It contains all the information about a particle, such
as an electron, including its position, momentum, and energy.
❖ In Hartree-Fock (HF) and Density Functional Theory (DFT),
wave functions are used to approximate electron behavior in
atoms and molecules.
❖ In Molecular Orbital Theory (MO),
molecular wave functions
describe electrons delocalized
across the molecule.
 Some definitions
❖ In quantum mechanics, an
operator is mathematical function
that acts on a wave function ψ to
extract physical information
(energy, momentum, or position).
❖ Operators are essential because
observable quantities in quantum
mechanics (like energy and
momentum) correspond to
operators rather than simple
numerical values.
 Quantum Mechanical Operator

❖ Any observation in quantum mechanics is represented by

an operator (energy, momentum, or position).
❖ The Hamiltonian operator represents the total energy of a
quantum system (kinetic + potential):

❖ ∇2 is the Laplacian operator (describes kinetic energy)

❖ V(r) is the potential energy
❖ ℏ is the reduced Planck’s constant.
 Many Particle Problem in solid

❖ Find the ground state for a collection of atoms by solving

the Schrodinger wave equation:

K.E Columb Interaction

❖ Separation of Variables (Born-Oppenheimer Approximation)
❖ Since the nucleus is much heavier than the electron (M≫me​),
we assume the nucleus is stationary. This allows us to separate
the wavefunction:
 Many Particle Problem in solid

❖ This simplifies solving the Schrödinger equation, as we

first solve for electronic motion while treating the nucleus
as fixed, then solve for nuclear motion separately.
 Many Particle Problem in solid: Solve the Schrodinger
wave equation for electrons
❖ In a solid, electrons interact with both atomic nuclei and other
electrons, making the many-body Schrödinger equation
complex to solve exactly. The general form of the equation for
N interacting electrons in a periodic potential is:

❖ H^ is the Hamiltonian operator,

❖ Ψ(r1,r2,...,rN)Ψ(r1​,r2​,...,rN​) is many-electron wavefunction,
❖ E is the total energy of the system,
❖ ri are the coordinates of each electron.
The electronic Hamiltonian operator consist of three terms

❖ The first term represents the kinetic energy of each

electron,
❖ The second term accounts for the periodic potential
due to the crystal lattice (nuclei),
❖ The third term represents electron-electron Coulomb
repulsion, which makes the problem difficult to solve exactly.
 Many Particle Problem in solid

❖ CO2; 6+16 = 22 electrons

- Three spatial coordinates per electronic position
- Schrodinger equation becomes 66 dimensional problems

❖ Pb nanoclusters (82 electrons per atom)

- 100 atoms → 8200 electrons
- Schrodinger equation becomes 24,600 dimensional
problems.
Solving the Schrodinger wave equation for materials like
this is particularly a bit of hassle.
 Density Functional Theory

❖ From wave function to electron density.

❖ N (r) = Ψ* (r1,r2…….rN) Ψ (r1,r2,…..rN) 3N dimension
reduces to 3
❖ Consider the jth electron is treated as a point charge in the
field of al the other electrons. This simplifies the many-
electron problem to many-one electron problems.
❖ Ψ(r1,r2,...,rN) = Ψ1(r1)*Ψ2(r12)*Ψ3(r3)….. ΨN(rN​) ​)
❖ Define the electron density in terms of all the single electrons
wave function.
 Density Functional Theory
❖ From wave function to electron density.
❖ N (r) = Ψ* (r1,r2…….rN) Ψ (r1,r2,…..rN) 3N dimension
reduces to 3
❖ Consider the jth electron is treated as a point charge in the
field of al the other electrons. This simplifies the many-
electron problem to many-one electron problems.
❖ Ψ(r1,r2,...,rN) = Ψ1(r1​)*Ψ2(r12​)*Ψ3(r3​)….. ΨN(rN​) ​)
❖ Define the electron density in terms of all the single electrons
wave function.
 Density Functional Theory (DFT):

Hohenberg-Kohn Theorems: (1964)

Theorem 1: The ground-state properties (energy) is a unique
functional of the electron density.
E=E[n(r)]

Theorem 2: The electron density that minimizes the energy of

the overall functional is the true ground state electron density.
 Density Functional Theory (DFT):
❖ In DFT, the total energy of a system is expressed as a
functional of the electron density n(r), rather than the many-
electron wave function.
❖ The energy functional E[n] is divided into different
contributions that account for kinetic energy, external
potential energy, and electron-electron interactions.
❖ The total energy of an N-electron system is given by the
energy functional:
❖ where: T[n] is the kinetic energy functional, Vext​[n] is the
interaction with the external potential, Vee​[n] is the electron-
electron interaction energy.
 Density Functional Theory (DFT):
❖ Since exact form of T[n] and Vee[n] is unknown for interacting
systems, Kohn-Sham DFT approximates these terms.
Exchange-Correlation Functional:
Since the exact exchange-correlation energy is unknown, DFT
approximates it using exchange-correlation functionals such as:
• Local Density Approximation (LDA): Assumes exchange-
correlation depends only on local electron density.
• Generalized Gradient Approximation (GGA): Includes
density gradients for improved accuracy.
• Hybrid Functionals (e.g., B3LYP): Mix a portion of exact Hartree-
Fock exchange with GGA for better accuracy in molecular systems.
 The Kohn Sham Scheme
❖ LDA assumes that the exchange-correlation energy per electron at a
given point depends only on the local electron density n(r).
❖ It is derived from the uniform electron gas model, where electrons are
spread evenly in space.
❖ GGA improves upon LDA by including the gradient (spatial variation)
of the electron density ∇n(r).
❖ It recognizes that in real materials and molecules, electron density is
not uniform, especially near nuclei and in bonding regions.
❖ Hybrid functionals combine GGA functionals with a portion of exact
exchange energy from Hartree-Fock (HF) theory.
❖ This improves the accuracy for molecular systems, especially in
predicting reaction barriers, vibrational frequencies, and band gaps.
 Final Thoughts

❖ LDA is the simplest and fastest, but least accurate for

molecules and semiconductors.

❖ GGA improves on LDA by considering density variations,

making it more accurate for chemical reactions and surfaces.

❖ Hybrid functionals (e.g., B3LYP) further improve accuracy by

incorporating Hartree-Fock exchange, but at a higher
computational cost.