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arXiv · 2001.09218

EOM-CC Methods with Approximate Triple Excitations for NEXAFS and XPS

Devin A. Matthews
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Abstract

A number of iterative and perturbative approximations to the full equation-of-motion coupled cluster method with single, double, and triple excitations (EOM-CCSDT) are evaluated in the context of calculating the K-edge core-excitation and core-ionization energies of several small molecules. Several of these methods are found to accurately reproduce the full EOM-CCSDT energies well, in particular the EOM-CCSD* method which, when using the core-valence separation (CVS) ansatz, scales rigorously with the sixth power of molecular size. The EOM-CCSDR(3) method, which has been used previously to include triples effects in a cost-effective manner was found to perform rather poorly, although the precise cause has not been determined. These results highlight that very accurate NEXAFS and XPS spectra for molecules with first-row atoms can be computed at a cost not much larger than that for EOM-CCSD.

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Devin A. Matthews. 2020-01-24. EOM-CC Methods with Approximate Triple Excitations for NEXAFS and XPS. https://doi.org/10.1080/00268976.2020.1771448

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