Force Constants and Dipole-Moment Derivatives of Molecules from Perturbed Hartree–Fock Calculations. I

Abstract

General expressions for the force constants and dipole-moment derivatives of molecules are derived, and the problems arising in their practical application are reviewed. Great emphasis is placed on the use of the Hartree–Fock function as an approximate wavefunction, and a number of its properties are discussed and re-emphasised. The main content of this paper is the development of a perturbed Hartree–Fock theory that makes possible the direct calculation of force constants and dipole-moment derivatives from SCF–MO wavefunctions. Essentially the theory yields ∂φi / ∂RJα, the derivative of an MO with respect to a nuclear coordinate.