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Updated: Jul 15, 2026

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
Published on: April 8, 2020
Reduced multireference coupled-cluster method: barrier heights for heavy atom transfer, nucleophilic substitution,
1Department of Applied Mathematics, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1.
Abstract:
The recently developed reduced multireference coupled-cluster method with singles and doubles (RMR CCSD) that is perturtatively corrected for triples [RMR CCSD(T)] is employed to compute the forward and reverse barrier heights for 19 non-hydrogen-transfer reactions. The method represents an extension of the conventional single-reference (SR) CCSD(T) method to multireference situations. The results are compared with a benchmark database, which is essentially based on the SR CCSD(T) results. With the exception of seven cases, the RMR CCSD(T) results are almost identical with those based on SR CCSD(T), implying the abatement of MR effects at the SD(T) level relative to the SD level. Using the differences between the RMR CCSD(T) and CCSD(T) barrier heights as a measure of MR effects, modified values for barrier heights of studied reactions are given.
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