Collect. Czech. Chem. Commun. 2007, 72, 100-120

Correction for Triples in Reduced Multireference Coupled-Cluster Approaches

Josef Paldus* and Xiangzhu Li

Department of Applied Mathematics, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1


The performance of the recently proposed version of the reduced multireference (RMR) coupled-cluster (CC) method with singles and doubles (SD), which employs a modest-size configuration interaction wave function as an external source for a small subset of approximate connected three- and four-body cluster amplitudes that are primarily responsible for the nondynamic correlation effects, and which has been perturbatively corrected for the remaining triples along the same line as in the standard CCSD(T) method (Li X., Paldus J.: J. Chem. Phys. 2006, 124, 174101), referred to by the acronym RMR CCSD(T), is being tested by evaluating equilibrium spectroscopic constants for a demanding system of the beryllium dimer, as well as by computing atomization energies for several di- and triatomics. The focus is on the equilibrium properties, since it has been demonstrated earlier that the RMR CCSD method corrects well for the nondynamic correlation in bond-breaking situations. We find that in all the cases we have examined, the RMR CCSD(T) method does in fact improve the performance of CCSD(T) even in the vicinity of the equilibrium geometry. For states possessing a moderate multireference character, the improvement in computed thermochemical properties relative to CCSD(T) amounts to a few kJ/mol, a meaningful amount when striving for chemical accuracy.

Keywords: Coupled-cluster method; Externally-corrected coupled-cluster methods; Reduced multireference coupled-cluster method; Correction for triples; Beryllium dimer; Atomization energies; Size-extensivity; Ab initio calculations.

References: 147 live references.