Calculation of wavefunctions and frequencies for noninfinitesimal vibrations. Comparison of various methods using ab initio CI potential curves

Abstract

Three computational methods employing different means of representing molecular potentials are used to obtain wavefunctions and energy levels for noninfinitesimal vibrations. An interpolation scheme based on a cubic spline fitting procedure is introduced to supplement the CI energy results obtained explicitly in actual calculations. As long as a representative set of potential points is available it is found that the results of all three methods (two of variational and one of numerical integration type) are quite consistent, for both bending and stretching vibrations of ground and electronically excited states (examples for HCN and O2 are considered). In addition a comparison of one- and two-dimensional bending vibrational treatments is made. © 1979.