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Updated: Nov 24, 2025

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
Published on: April 8, 2020
A route to improving RPA excitation energies through its connection to equation-of-motion coupled cluster theory
Varun Rishi1, Ajith Perera2, Rodney J Bartlett2
1Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
Abstract:
We revisit the connection between equation-of-motion coupled cluster (EOM-CC) and random phase approximation (RPA) explored recently by Berkelbach [J. Chem. Phys. 149, 041103 (2018)] and unify various methodological aspects of these diverse treatments of ground and excited states. The identity of RPA and EOM-CC based on the ring coupled cluster doubles is established with numerical results, which was proved previously on theoretical grounds. We then introduce new approximations in EOM-CC and RPA family of methods, assess their numerical performance, and explore a way to reap the benefits of such a connection to improve on excitation energies. Our results suggest that addition of perturbative corrections to account for double excitations and missing exchange effects could result in significantly improved estimates.
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