BENCHMARK CALCULATIONS WITH CORRELATED MOLECULAR WAVE FUNCTIONS .10. COMPARISON WITH EXACT MP2 CALCULATIONS ON NE, HF, H2O, AND N-2

摘要

The convergence of the MP2 valence correlation energy and pair energies for the correlation consistent basis sets has been investigated. Ne, HF, H2O, and N-2 were studied. For all of these molecules, accurate MP2 correlation and pair energies are available from the recent MP2-R12. calculations of W. Klopper [J. Chem. Phys. 102, 6168 (1995)]. The magnitudes of the calculated MP2 valence correlation and pair energies are found to increase systematically with increasing basis set size, with the cc-pV6Z basis set yielding 97.4%-98.3% of the MP2 valence correlation energy. A detailed analysis of the results for Ne reveals that the error due to truncation of the radial functions in the cc-pV6Z set is comparable to that due to neglect of higher angular momentum functions. Procedures for extrapolating the results to the complete basis set limit have also been investigated. (C) 1997 American Institute of Physics. [References: 31]