Lecture

Hartree-Fock Equations: Derivation and Solutions

Graph Chat

Chat with Graph Search

Ask any question about EPFL courses, lectures, exercises, research, news, etc. or try the example questions below.

DISCLAIMER: The Graph Chatbot is not programmed to provide explicit or categorical answers to your questions. Rather, it transforms your questions into API requests that are distributed across the various IT services officially administered by EPFL. Its purpose is solely to collect and recommend relevant references to content that you can explore to help you answer your questions.

In course

CH-353: Introduction to electronic structure methods

Repetition of the basic concepts of quantum mechanics and main numerical algorithms used for practical implementions. Basic principles of electronic structure methods:Hartree-Fock, many body perturbation theory, configuration interaction, coupled-cluster t ...

Description

This lecture covers the derivation of the Hartree-Fock equations, focusing on the self-interaction-free Hartree-Fock method, the Fock equation, and the Roothaan equations. It explains the iterative process to find the Hartree-Fock wavefunction and the matrix form of the Roothaan equations.

This video is available exclusively on Mediaspace for a restricted audience. Please log in to MediaSpace to access it if you have the necessary permissions.

Watch on Mediaspace

Instructor

Ursula Röthlisberger

U. Röthlisberger was born in Solothurn (Switzerland). In 1988 she made her diploma in Physical Chemistry in the group of Prof. Ernst Schumacher at the University of Berne (Switzerland). Her Ph.D. thesis was done in collaboration with Dr. Wanda Andreoni at the IBM Zurich Research Laboratory in Rüschlikon. After finishing her Ph.D in 1991 she spent some time as a postdoctoral research assistant at the IBM Research Lab. From 1992-1995 she was a postdoctoral research assistant in the group of Prof. Michael L. Klein at the University of Pennsylvania in Philadelphia (USA). In 1994 she was awarded an advanced researcher fellowship (Profil 2) from the Swiss National Science Foundation. Before starting her Profile 2-fellowship she spent another year as postdoctoral research assistant in the group of Prof. Michele Parrinello at the Max-Planck-Institute for Solid State Physics in Stuttgart, Germany. In 1996 she moved as Profile 2-fellow to the ETH in Zurich, hosted by the group of Prof. Wilfred F. van Gunsteren. In 1997 she became Assistant Professor of Computer-Aided Inorganic Chemistry at the ETH Zurich.

Official source

Related concepts (25)

Multi-configurational self-consistent field

Multi-configurational self-consistent field (MCSCF) is a method in quantum chemistry used to generate qualitatively correct reference states of molecules in cases where Hartree–Fock and density functional theory are not adequate (e.g., for molecular ground states which are quasi-degenerate with low-lying excited states or in bond-breaking situations). It uses a linear combination of configuration state functions (CSF), or configuration determinants, to approximate the exact electronic wavefunction of an atom or molecule.

Fock state

In quantum mechanics, a Fock state or number state is a quantum state that is an element of a Fock space with a well-defined number of particles (or quanta). These states are named after the Soviet physicist Vladimir Fock. Fock states play an important role in the second quantization formulation of quantum mechanics. The particle representation was first treated in detail by Paul Dirac for bosons and by Pascual Jordan and Eugene Wigner for fermions.

Configuration interaction

Configuration interaction (CI) is a post-Hartree–Fock linear variational method for solving the nonrelativistic Schrödinger equation within the Born–Oppenheimer approximation for a quantum chemical multi-electron system. Mathematically, configuration simply describes the linear combination of Slater determinants used for the wave function. In terms of a specification of orbital occupation (for instance, (1s)2(2s)2(2p)1...), interaction means the mixing (interaction) of different electronic configurations (states).

Triangular matrix

In mathematics, a triangular matrix is a special kind of square matrix. A square matrix is called if all the entries above the main diagonal are zero. Similarly, a square matrix is called if all the entries below the main diagonal are zero. Because matrix equations with triangular matrices are easier to solve, they are very important in numerical analysis. By the LU decomposition algorithm, an invertible matrix may be written as the product of a lower triangular matrix L and an upper triangular matrix U if and only if all its leading principal minors are non-zero.

Diagonal matrix

In linear algebra, a diagonal matrix is a matrix in which the entries outside the main diagonal are all zero; the term usually refers to square matrices. Elements of the main diagonal can either be zero or nonzero. An example of a 2×2 diagonal matrix is , while an example of a 3×3 diagonal matrix is. An identity matrix of any size, or any multiple of it (a scalar matrix), is a diagonal matrix. A diagonal matrix is sometimes called a scaling matrix, since matrix multiplication with it results in changing scale (size).

Related lectures (64)

Hartree-Fock Method: Theory and Applications

Explores the Hartree-Fock method in quantum chemistry, emphasizing the variational principle and self-consistent solutions.

Matrix Form and IO Analysis

Covers Material Flow Analysis in matrix form and Input-Output Analysis, exploring balance equations, transfer coefficients, GHG emissions, and economic impact.

Quantum Chemical Electronic Structure Methods

Explores quantum chemical electronic structure methods, including basis sets and the Hartree-Fock method.

Electronic Structure Methods

Covers basis set errors, Hartree-Fock methods, electron correlation, configuration interaction, and composite approaches in computational chemistry.

Hartree-Fock Method: Basis Sets and Quantum Chemistry