Journal
THEORETICAL CHEMISTRY ACCOUNTS
Volume 105, Issue 3, Pages 182-196Publisher
SPRINGER
DOI: 10.1007/s002140000196
Keywords
coupled-cluster methods; CCSDT; CCSDT-n; many-body perturbation theory analysis atomization energies
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CCSDT-n methods (n = 1, ..., 4) are analyzed in terms of many-body perturbation theory and compared with CCSD, CCSD(T), and CCSDT. Correlation terms, which are introduced at each CCSDT-n level are identified and discussed with regard to their importance for the total energy. CCSDT-la represents the strongest improvement of CCSD since it covers 75% of the T terms added at the CCSDT level. At CCSDT-2 and CCSDT-3, only partial energy terms are added where the positive ..TQ.. coupling terms at CCSDT-2 are more important than the slightly negative ..TTS terms at CCSDT-3. CCSDT-4 leads to new ..TT.. coupling effects, which lower the energy. Calculated CCSDT-n/correlation-consistent polarized-valence triple-zeta spectra reveal that the energy changes caused by CCSDT-2, CCSDT-3, CCSDT-4. and CCSDT largely cancel each other out; however, because of a dependence of these contributions on electron clustering the importance of these effects for the correct description of certain chemical reactions must be considered. It is shown that CCSDT-1 las well as all other CCSDT-n) calculations lead to atomization energies as accurate as G2 values, where this result reflects the importance of including at least some of the T effects.
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