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Updated: Apr 23, 2026

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
Published on: April 8, 2020
The Dose Makes the Poison: Perturbative Steps toward the Ultimate Linearized Coupled Cluster Method
Sylvia J Bintrim1, Ella R Ransford1, Kevin Carter-Fenk1
1Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania15218, United States.
Abstract:
"Addition-by-subtraction" coupled cluster (CC) approaches provide a promising approach to treating the difficult strong correlation problem by simplifying the standard CC equations. In a separate vein, linearized CC methods have drawn interest for their lower computational cost, increased parallelizability, and favorable properties for extension to the excited state-but the inclusion of ring/crossed-ring terms causes singularities even for single bond breaking. A linearized, addition-by-subtraction CC method called linearized ladder CCD (linLCCD) removes these terms to avoid divergences, but linLCCD underestimates dynamical correlation. Herein we resolve this deficiency of linLCCD by introducing a linearized external coupled cluster perturbation theory that adds a second-order ring/crossed-ring correction back into a linLCCD reference wave function. Our resultant xlinCCD(2) method is regular and yields comparable results to linearized CCD in weakly correlated regimes.
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