ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A series of complete coupled-cluster singles, doubles, and triples (CCSDT) calculations have been performed with Hartree-Fock (HF) and Brueckner (B) orbitals. Calculations have been performed with a double-zeta plus polarization basis set on the H2O, SiH2, NH2, BeO, C2, CN+, and BN molecules. Calculations on H2O and SiH2 at equilibrium and stretched geometries show negligible difference between HF-and B-CCSDT energies. This is also true for NH2, except when the bonds have been stretched to twice their equilibrium values, at which point there is about a 2.5 milli-Hartree (mEh) difference. Calculations on the isoelectronic systems BeO, C2, CN+, and BN were performed at equilibrium geometries. Even though these systems have large T1 amplitudes, the difference between HF- and B-CCSDT energies is only about 1 mEh. For the CCSD method and the CCSD(T) method, which includes triple excitations in an approximate, noniterative manner, however, somewhat larger differences are observed between and HF-and B-CC results. Finally, some properties of BN were computed using HF- and B-CC methods. There are quite small differences between the HF- and B-CCSDT results, but significantly larger ones for the more approximate CCSD and CCSD(T) methods. For this difficult system, where the CCSD(T) approximation seems to be inadequate for HF orbitals, the use of Brueckner orbitals improves the agreement of CCSD(T) with CCSD(T) substantially for re and we, although the difference for μ is unaffected. © 1994 John Wiley & Sons, Inc.
Additional Material:
6 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560520820
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