Communication: Adjusting charge transfer state energies for configuration interaction singles: without any parameterization and with minimal cost

The Journal of Chemical Physics
Xinle LiuJoseph E Subotnik

Abstract

In a recent article, we showed that configuration interaction singles (CIS) has a systematic bias against charge-transfer (CT) states: CT vertical excitation energies are consistently too high (by 1-2 eV) as compared with non-CT energies [J. E. Subotnik, J. Chem. Phys. 137, 071104 (2011)]. We now show that this CIS error can be corrected approximately by performing a single Newton-Raphson step to reoptimize orbitals, thus establishing a new set of orbitals which better balances ground and excited state energies. The computational cost of this correction is exactly that of one coupled-perturbed Hartree-Fock calculation, which is effectively the cost of the CIS calculation itself. In other words, for twice the computational cost of a standard CIS calculation, or roughly the same cost as a linear-response time-dependent Hartree-Fock calculation, one can achieve a balanced, size-consistent description of CT versus non-CT energies, ideally with the accuracy of a much more expensive doubles CIS(D) calculation.

References

Apr 20, 2005·The Journal of Chemical Physics·Johannes NeugebauerTomasz A Wesolowski
Aug 12, 2006·Physical Chemistry Chemical Physics : PCCP·Yihan ShaoMartin Head-Gordon
Nov 23, 2006·The Journal of Chemical Physics·Neepa T Maitra, David G Tempel
Feb 6, 2008·The Journal of Chemical Physics·Michael J G PeachDavid J Tozer
Mar 5, 2008·The Journal of Chemical Physics·Jeng-Da Chai, Martin Head-Gordon
May 27, 2008·The Journal of Chemical Physics·Thomas M HendersonGustavo E Scuseria
Jul 24, 2008·The Journal of Chemical Physics·Mary A Rohrdanz, John M Herbert
Sep 11, 2009·The Journal of Chemical Physics·Paul WigginsDavid J Tozer
Jan 9, 2010·Annual Review of Physical Chemistry·Roi BaerUlrike Salzner
Aug 24, 2010·The Journal of Chemical Physics·Zhi-Qiang You, Chao-Ping Hsu
May 1, 2007·Journal of Chemical Theory and Computation·R J Magyar, S Tretiak

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Citations

Jun 20, 2013·The Journal of Physical Chemistry. a·Vincent A Spata, Spiridoula Matsika
Apr 30, 2013·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·JingXin LiangSpiridoula Matsika
Mar 11, 2014·Journal of Chemical Theory and Computation·Xinle Liu, Joseph E Subotnik
May 3, 2014·The Journal of Chemical Physics·Alisa SolovyevaJohannes Neugebauer
Sep 20, 2016·Journal of Chemical Theory and Computation·Miquel Huix-Rotllant, Nicolas Ferré
Sep 19, 2014·Physical Chemistry Chemical Physics : PCCP·Nicholas J MayhallMartin Head-Gordon
Sep 9, 2018·The Journal of Chemical Physics·Jacqueline A R Shea, Eric Neuscamman
Aug 24, 2017·The Journal of Chemical Physics·Chenyang LiFrancesco A Evangelista
Sep 5, 2019·The Journal of Physical Chemistry Letters·Piotr de Silva
Mar 13, 2019·Journal of Chemical Theory and Computation·Hung-Hsuan LinChao-Ping Hsu
Dec 12, 2018·Journal of Chemical Theory and Computation·Nick S Blunt, Eric Neuscamman

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