Computation of molecular vibrational frequencies using anomalous harmoniclike potentials.
The instabilities of Hartree-Fock (HF) solutions at or near the equilibrium geometry of symmetric molecular species imply the existence of broken-symmetry solutions having a lower energy than the corresponding symmetry-adapted ones. Moreover, the distortion of the nuclear framework along the normal modes that are implied by such broken-symmetry solutions results in an anomalous or even singular behavior in the corresponding cuts of the potential energy surface (PES). Using such HF solutions as a reference, these anomalies propagate to a post-HF level and make it impossible to determine reliable harmonic or fundamental vibrational frequencies for such modes by relying on either numerical or analytical differentiation of the PES, requiring instead a numerical integration of the Schrodinger equation for the nuclear motion. This, in turn, requires a detailed knowledge on the PES in a wide range of geometries, necessitating a computation of the potential energy function in a large number of points. We present an alternative approach to this problem, referred to as the integral averaging method (IAM), which facilitates this task by significantly reducing the number of geometries for which one has to compute the potential energy while yielding results of practically the same accuracy as the solution of the Schrodinger equation. The IAM is applied to several ABA-type triatomics and to the allyl radical, whose asymmetric stretching mode potential suffers from an anomalous behavior due to the spin-preserving instabilities in restricted open-shell HF solutions.
Li
Xiangzhu
X
Department of Applied Mathematics, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada. xli@scienide.uwaterloo.ca
Paldus
Josef
J