Hylleraas Variational Perturbation Theory: Application to Correlation Problems in Molecular Systems

Authors

Robert J. Cave, Harvey Mudd CollegeFollow
Ernest R. Davidson, Indiana University - Bloomington

Document Type

Article

Department

Chemistry (HMC)

Publication Date

5-1-1988

Abstract

Hylleraas variational perturbation theory is applied through second order in energy to estimate the correlation energy in several molecular systems. The specific choices for H₀ and V which are made lead to equations nearly identical to the multireference linearized coupled‐cluster method of Laidig and Bartlett. The results obtained are in virtually exact agreement where comparisons have been made. Results from test calculations are presented for BeH₂, CH₂, and C₂H₄. In addition, the utility of perturbation theory for selecting correlating configurations is examined. This procedure is found to be quite accurate while significantly reducing the size of the system of linear equations to be solved.

Comments

© 2011 American Institute of Physics

Rights Information

© 1988 American Institute of Physics

DOI

10.1063/1.454535

Recommended Citation

Hylleraas variational perturbation theory: Application to correlation problems in molecular systems. Robert J. Cave and Ernest R. Davidson, J. Chem. Phys. 88, 5770 (1988), DOI: 10.1063/1.454535