Scribd
Upload
43 views17 pages

CSE Lec 7-8

The document provides an overview of computational chemistry tools, focusing on classical and quantum mechanical methods, particularly the Hartree-Fock (HF) method and Density Functional Theory (DFT). It discusses the limitations of HF, including its neglect of electron correlation and computational expense, while highlighting DFT's advantages in efficiency and applicability to large systems. The document also outlines the fundamental theorems of DFT, emphasizing the relationship between electron density and ground-state properties.

Uploaded by

khansashahzadi111
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
43 views17 pages

CSE Lec 7-8

The document provides an overview of computational chemistry tools, focusing on classical and quantum mechanical methods, particularly the Hartree-Fock (HF) method and Density Functional Theory (DFT). It discusses the limitations of HF, including its neglect of electron correlation and computational expense, while highlighting DFT's advantages in efficiency and applicability to large systems. The document also outlines the fundamental theorems of DFT, emphasizing the relationship between electron density and ground-state properties.

Uploaded by

khansashahzadi111
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 17

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

CHEMISTRY

Lecture 7-8

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


Quantum Mechanics”, Errol Lewars, Kluwer Academic Publishers, 2004.
T O O L S OF CO M P UTATI O NAL
CHEMISTRY

1. Classical Mechanical Method


2. Quantum Mechanical Method
a. Ab initio or Hartee-Fock (HF) Method
❖ HF is just an approximation. It assumes that each
electron interacts with an average charge distributiondue to the
other electrons.

❖ Computationally expensive.

❖ Solves the Schrödinger equation approximately by assuming


electrons move in an average potential created by all other
electrons (mean-field approximation).

❖ Neglects electron correlation (interaction between electrons),


making it less accurate for systems with strong electron
interactions.
a. Ab initio or Hartee-Fock (HF) Method

❖ Instead of solving for the exact wavefunction of a multi-


electron system, HF assumes that each electron moves in
an average electrostatic field created by all other electrons.

❖ The total wavefunction is represented as a single Slater


determinant, ensuring the Pauli exclusion principle is
satisfied.

❖ Mathematical Formulation

❖ The HF equation for an electron in orbital ϕi is: Fϕi = ϵiϕi

❖ where F is the Fock operator, and ϵi are the orbital energies.


a. Ab initio or Hartee-Fock (HF) Method
❖ The Fock operator includes:

❖ Kinetic energy of the electron

❖ Nuclear attraction potential

❖ Electron-electron repulsion (averaged as a mean field)

❖ Exchange interaction (due to the antisymmetry of the wavefunction).

❖ Limitations of HF Approximation

No Electron Correlation: Overestimates total energy.

Computationally Expensive for Large Systems: Scales as O (N⁴ - N⁷).

Fails for Strongly Correlated Systems: Such as transition metal complexes.


a. Post-Hartree-Fock Methods
❖ This method improve upon the Hartree-Fock approximation
by explicitly accounting for electron correlation:

❖ Møller-Plesset Perturbation Theory (MP2, MP3, etc.): Adds


corrections to HF results by including electron correlation effects.

❖ Configuration Interaction (CI): Considers multiple electronic


configurations to account for electron correlation.

❖ Coupled Cluster (CC, CCSD, CCSD(T)): Provides highly accurate


results by including correlations systematically, wavefunction
methods.

❖ Density Functional Theory (DFT): Uses functionals to approximate


correlation.
Density Functional Theory (DFT):
❖ A separate, often more computationally efficient approach.
❖ Although not strictly "ab-initio" in the traditional sense.
❖ It is frequently used due to its balance between accuracy and
efficiency.
Applications of Ab-Initio Methods:
❖ Predicting Molecular Properties
❖ Spectroscopic Analysis
❖ Reaction Mechanisms
❖ Potential Energy Surfaces
❖ Electronic Structure
Limitations:
1. Computationally expensive, especially for large systems.
2. Requires significant computational resources for high-level calculations.
3. May not be suitable for modeling large biological systems or polymers
directly.
Density Functional Theory (DFT):
❖ It is widely used computational quantum mechanical method
for investigating the electronic structure of many-body systems,
particularly atoms, molecules, and solids.

❖ It is commonly applied in chemistry, physics, and materials


science to predict properties such as molecular geometries,
reaction energies, electronic band structures, and charge
distributions.
❖ Advantages:
Computationally efficient compared to wavefunction-based
methods (e.g., MP2, CCSD).
Can handle large molecular systems and solids.
Provides reasonable accuracy for structural, electronic, and
energetic properties.
Density Functional Theory (DFT):
❖ To solve many body problems by Schrödinger's equation.
❖ Only upto one electron problem we can solve Schrödinger's
equation exactly.
❖ It is very hectic to solve the Schrödinger's equation for a N-
body system.
❖ We must involve some approximation to solve the problem a
method to obtain an approximate solution to the
Schrödinger's equation of a many body system is DFT.
We discuss two parts:
Part 1: fundamentals of density functional theory, solving many
body Schrödinger equation, Applications of DFT.
Part 2: doing DFT calculations - practical aspect.
Density Functional Theory (DFT):

1. Electron Density as the Fundamental Variable:


❖ Unlike wavefunction-based methods (e.g., Hartree-Fock),
DFT focuses on the electron density, ρ(r), rather than the
many-electron wavefunction.

❖ The Hohenberg-Kohn Theorems (1964) state that the


ground-state properties of a system are uniquely
determined by its electron density.
Density Functional Theory (DFT):

2. Kohn-Sham Equations (1965):

❖ Walter Kohn and Lu Jeu Sham introduced the Kohn-Sham

(KS) equations, which reformulate the problem into a system

of non-interacting electrons moving in an effective potential.

❖ The effective potential includes contributions from the

external potential, classical Coulomb interaction, and

exchange-correlation effects.
Density Functional Theory (DFT):
3. 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.
HOHENBERG – KOHN THEOREMS

Based on two fundamental theorems:

Theorem 1: The external potential or the ground state energy


E is a unique functional of 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.
Theorem 1 of Density Functional Theory (DFT)

❖ The first fundamental theorem of Density Functional Theory


(DFT) states:
❖ "The external potential Vext​(r) and, consequently, the ground-
state energy E of a many-electron system, is a unique
functional of the electron density n(r).”
❖ Mathematically, this can be expressed as:

E=E[n(r)]
where E is the total ground-state energy, is a functional of the
electron density n(r).
Theorem 1 of Density Functional Theory (DFT)

❖ This theorem was established by Hohenberg and Kohn

(1964), forming the foundation of DFT.

❖ It proves that for a system of interacting electrons in an

external potential Vext(r), the ground-state electron density n(r)

uniquely determines Vext(r) (up to an additive constant).

❖ Since Vext(r) defines the Hamiltonian, all properties of the

system (such as total energy) are uniquely determined by n(r).


Theorem 1 of Density Functional Theory (DFT)

❖ This theorem was established by Hohenberg and Kohn


(1964), forming the foundation of DFT.
❖ It proves that for a system of interacting electrons in an
external potential Vext(r), the ground-state electron density n(r)
uniquely determines Vext(r) (up to an additive constant).
❖ Since Vext(r) defines the Hamiltonian, all properties of the
system (such as total energy) are uniquely determined by n(r).
❖ Here, the ground-state energy E is a functional of the electron
density n(r), meaning that if we know n(r), we can determine
E.

You might also like