Accurate computational thermochemistry from explicitly correlated coupled-cluster theory

Wim Klopper • Rafal A. Bachorz • Christof Hättig • David P. Tew

Theor. Chem. Acc. 126, 289-304 (2010).
Received: 8 December 2009 / Accepted: 5 Februar 2010

Explicitly correlated coupled-cluster theory has developed into a valuable computational tool for the calculation of electronic energies close to the limit of a complete basis set of atomic orbitals. In particular at the level of coupled-cluster theory with single and double excitations (CCSD), the space of double excitations is quickly extended towards a complete basis when Slater-type geminals are added to the wave function expansion. The purpose of the present article is to demonstrate the accuracy and efficiency that can be obtained in computational thermochemistry by a CCSD model that uses such Slater-type geminals. This model is denoted as CCSD(F12), where the acronym F12 highlights the fact that the Slater-type geminals are functions f(r (12)) of the interelectronic distances r (12) in the system. The performance of explicitly correlated CCSD(F12) coupled-cluster theory is demonstrated by computing the atomization energies of 73 molecules (containing H, C, N, O, and F) with an estimated root-mean-square deviation from the values compiled in the Active Thermochemical Tables of sigma = 0.10 kJ/mol per valence electron. To reach this accuracy, not only the frozen-core CCSD basis-set limit but also high-order excitations (connected triple and quadruple excitations), core-valence correlation effects, anharmonic vibrational zero-point energies, and scalar and spin-orbit relativistic effects must be taken into account.

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