Roothaan equations

From Wikipedia, the free encyclopedia

The Roothaan equations are a representation of the Hartree-Fock equation in a non orthonormal basis set which can be of Gaussian-type or Slater-type. It applies to closed-shell molecules or atoms where all molecular orbitals or atomic orbitals, respectively, are doubly occupied. This is generally called Restricted Hartree-Fock theory.

The method was developed independently by Clemens C. J. Roothaan and George G. Hall in the early 1950s, and are thus sometimes called the Roothaan-Hall equations. The Roothaan equations can be written in the form of generalized eigenvalue problem

<math>\mathbf{F} \mathbf{C} = \mathbf{S} \mathbf{C} \mathbf{\epsilon}</math>

Where F is the so-called Fock matrix, C is a matrix of coefficients, S is the overlap matrix of the basis functions, and <math>\epsilon</math> is the (diagonal, by convention) matrix of orbital energies. In the case of an orthonormalised basis set the overlap matrix, S, reduces to the identity matrix.