The efficient evaluation of configuration interaction analytic energy second derivatives: Application to hydrogen thioperoxide, HSOH

Abstract

We present an efficient reformulation of the analytic configuration interaction (CI) energy second derivative. Specifically, the Z-vector method of Handy and Schaefer is used to avoid solving the second order coupled perturbed Hartree–Fock (CPHF) equations. We have incorporated translational–rotational invariance into the new method. We present a more efficient method for the evaluation of the Y matrix contribution. The procedure which has been implemented can accommodate very large basis sets and CI expansions for any general restricted Hartree–Fock (RHF) reference wave function. As a test case, we apply the new procedure to the HSOH molecule using a double zeta plus polarization basis set. This leads to 50 contracted Gaussian basis functions and 116 403 configurations in the CI expansion. Harmonic vibrational frequencies and infrared intensities are predicted for HSOH and its deuterated isotopomers. The analytic method described herein requires only 56% of the central processor unit time used by a numerical method.