Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 8, Issue 7, Pages 1524-1529Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.7b00381
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Funding
- European Research Council (ERC) [Marches - 278845]
- Region des Pays de la Loire in the framework of LumoMat project
- European Union [646176]
- French National Agency for Research [ANR-11-EQPX-0004]
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Developing ab initio approaches able to provide accurate excited-state energies at a reasonable computational cost is one of the biggest challenges in theoretical chemistry. In that framework, the Bethe-Salpeter equation approach, combined with the GW exchange-correlation self-energy, which maintains the same scaling with system size as TD-DFT, has recently been the focus of a rapidly increasing number of applications in molecular chemistry. Using a recently proposed set encompassing excitation energies of many kinds [J. Phys. Chem. Lett. 2016, 7, 586-591], we investigate here the performances of BSE/GW. We compare these results to CASPT2, EOM-CCSD, and TD-DFT data and show that BSE/GW provides an accuracy comparable to the two wave function methods. It is particularly remarkable that the BSE/GW is equally efficient for valence, Rydberg, and charge-transfer excitations. In contrast, it provides a poor description of triplet excited states, for which EOM-CCSD and CASPT2 clearly outperform BSE/GW. This contribution therefore supports the use of the Bethe-Salpeter approach for spin-conserving transitions.
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