Lecture 8Introduction to Density Functional Theory.ppt

Lecture 8:Introduction to Density Functional Theory Marie Curie Tutorial Series: Modeling Biomolecules December 6-11, 2004 Mark Tuckerman Dept. of Chemistry and Courant Institute of Mathematical Science 100 Washington Square East New York University, New York, NY 10003 Background 1920s: Introduction of the Thomas-Fermi model. 1964: Hohenberg-Kohn paper proving existence of exact DF. 1965: Kohn-Sham scheme introduced. 1970s and early 80s: LDA. DFT becomes useful. 1985: Incorporation of DFT into molecular dynamics Car-Parrinello Now one of PRL’s top 10 cited papers . 1988: Becke and LYP functionals. DFT useful for some chemistry. 1998: Nobel prize awarded to Walter Kohn in chemistry for development of DFT. Results methanol Lecture Summary Density functional theory is an exact reformulation of many-body quantum mechanics in terms of the probability density rather than the wave function The ground-state energy can be obtained by minimization of the energy functional E[n]. All we know about the functional is that it exists, however, its form is unknown. Kohn-Sham reformulation in terms of single-particle orbitals helps in the development of approximations and is the form used in current density functional calculations today. * External Potential: Total Molecular Hamiltonian: Born-Oppenheimer Approximation: √ Hohenberg-Kohn Theorem Two systems with the same number Ne of electrons have the same Te + Vee. Hence, they are distinguished only by Ven. Knowledge of |Ψ0 determines Ven. Let V be the set of external potentials such solution of yields a non degenerate ground state |Ψ0 . Collect all such ground state wavefunctions into a set Ψ. Each element of this set is associated with a Hamiltonian determined by the external potential. There exists a 1:1 mapping C such that C : V Ψ Hohenberg-Kohn Theorem part II Given an antisymmetric ground state wavefunction from the set Ψ, the ground-state density is given by Knowledge of n r