A full coupled-cluster singles and doubles model: The inclusion of disconnected triples

Journal of Chemical Physics - Tập 76 Số 4 - Trang 1910-1918 - 1982
George D. Purvis1, Rodney J. Bartlett1
1Quantum Theory Project, Department of Chemistry, University of Florida, Gainesville, Florida 32611

Tóm tắt

The coupled-cluster singles and doubles model (CCSD) is derived algebraically, presenting the full set of equations for a general reference function explicitly in spin–orbital form. The computational implementation of the CCSD model, which involves cubic and quartic terms, is discussed and results are reported and compared with full CI calculations for H2O and BeH2. We demonstrate that the CCSD exponential ansatz sums higher-order correlation effects efficiently even for BeH2, near its transition state geometry where quasidegeneracy efforts are quite large, recovering 98% of the full CI correlation energy. For H2O, CCSD plus the fourth-order triple excitation correction agrees with the full CI energy to 0.5 kcal/mol. Comparisons with low-order models provide estimates of the effect of the higher-order terms T1T2, T21T2, T31, and T41 on the correlation energy.

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Journal of Chemical Physics

Tập 76 Số 4

1910-1918

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