6533b7d2fe1ef96bd125f6d4

RESEARCH PRODUCT

Analytic calculation of the diagonal Born-Oppenheimer correction within configuration-interaction and coupled-cluster theory

Attila TajtiJürgen GaussJohn F. StantonPéter G. SzalayMihály Kállay

subject

ChemistryComputationDiagonalBorn–Oppenheimer approximationGeneral Physics and AstronomyConfiguration interactionsymbols.namesakeCoupled clusterQuantum electrodynamicsConvergence (routing)symbolsPhysical and Theoretical ChemistryAtomic physicsWave functionBasis set

description

Schemes for the analytic calculation of the diagonal Born-Oppenheimer correction (DBOC) are formulated and implemented for use with general single-reference configuration-interaction and coupled-cluster wave function models. Calculations are reported to demonstrate the convergence of the DBOC with respect to electron-correlation treatment and basis set as well as to investigate the size-consistency error in configuration-interaction calculations of the DBOC. The importance of electron-correlation contributions to the DBOC is illustrated in the computation of the corresponding corrections for the reaction energy and activation barrier of the F + H2 --FH + H reaction as well as of the atomization energy for trans-butadiene.

yearjournalcountryeditionlanguage
2006-10-14The Journal of Chemical Physics
https://doi.org/10.1063/1.2356465