Hartree-Fock Theory

Abstract

The chapter begins with an introduction of independent particle approximation. With this approximation, the system has been transformed into a pool of individual wavefunctions---one for each particle. Although the independent particle approximation is often a serious oversimplification, in many cases these individual wavefunctions are found to be useful in providing a great deal of insight into the chemical behavior of a molecule. The chapter also includes topics such as the Hartree method, the Hartree-Fock method, bosons and fermions, the Slater determinant, the Fock matrix and the formulation of elements of Fock matrix. We have included the Roothaan-Hall equation and Koopman's theorem in this chapter. In fact, Koopman's theorem can be used for the computation of approximate ionization energy. The chapter concludes with an introduction of electronic correlation. As usual, practice problems have been included at the end.