A quadratically convergent VBSCF method

Abstract

A quadratically convergent valence bond self-consistent field method is described where the simultaneous optimisation of orbitals and the coefficients of the configurations (VB structures) is based on a Newton-Raphson scheme. The applicability of the method is demonstrated in actual calculations. The convergence and efficiency are compared with the Super-CI method. A necessary condition to achieve convergence in the Newton-Raphson method is that the Hessian is positive definite. When this is not the case, a combination of the Super-CI and Newton-Raphson methods is shown to be an optimal choice instead of shifting the eigenvalues of the Hessian to make it positive definite. In the combined method, the first few iterations are performed with the Super-CI method and then the Newton-Raphson scheme is switched on based on an internal indicator. This approach is found computationally a more economical choice than using either the Newton-Raphson or Super-CI method alone to perform a full optimisation of the nonorthogonal orbitals.