Document Type

Article

Publication Date

2018

Abstract

We study the performance of the two-determinant (TD) coupled-cluster (CC) method which, unlike conventional ground-state single-reference (SR) CC methods, can, in principle, provide a naturally spin-adapted treatment of the lowest-lying open-shell singlet (OSS) and triplet electronic states. Various choices for the TD-CC reference orbitals are considered, including those generated by the multi-configurational self-consistent field method. Comparisons are made with the results of high-level SR-CC, equation-of-motion (EOM) CC, and multi-reference EOM calculations performed on a large test set of over 100 molecules with low-lying OSS states. It is shown that in cases where the EOMCC reference function is poorly described, TD-CC can provide a significantly better quantitative description of OSS total energies and OSS-triplet splittings.

Comments

A 12-month embargo was observed for this posting in accordance with the publisher and the research funding body.

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This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in volume 148 of J. Chem. Phys. and may be found at https://doi.org/10.1063/1.5025170.

DOI

10.1063/1.5025170

Source Publication

The Journal of Chemical Physics

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