α-CASSCF: An Efficient, Empirical Correction for SA-CASSCF To Closely Approximate MS-CASPT2 Potential Energy Surfaces

The Journal of Physical Chemistry Letters
James W SnyderTodd J Martinez

Abstract

Because of its computational efficiency, the state-averaged complete active-space self-consistent field (SA-CASSCF) method is commonly employed in nonadiabatic ab initio molecular dynamics. However, SA-CASSCF does not effectively recover dynamical correlation. As a result, there can be qualitative differences between SA-CASSCF potential energy surfaces (PESs) and more accurate reference surfaces computed using multistate complete active space second-order perturbation theory (MS-CASPT2). Here we introduce an empirical correction to SA-CASSCF that scales the splitting between individual states and the state-averaged energy. We call this the α-CASSCF method, and we show here that it significantly improves the accuracy of relative energies and PESs compared with MS-CASPT2 for the chromophores of green fluorescent and photoactive yellow proteins. As such, this method may prove to be quite valuable for nonadiabatic dynamics.

References

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Oct 16, 2003·Journal of the American Chemical Society·Chaehyuk KoTodd J Martínez
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Apr 14, 2009·Journal of Chemical Theory and Computation·Ivan S Ufimtsev, Todd J Martinez
Feb 1, 2008·Journal of Chemical Theory and Computation·Ivan S Ufimtsev, Todd J Martínez
Oct 27, 2016·The Journal of Chemical Physics·Filipe MenezesHans-Joachim Werner

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Citations

Sep 28, 2018·Faraday Discussions·Jiří SuchanPetr Slavíček
May 21, 2019·Physical Chemistry Chemical Physics : PCCP·Benjamin G LevineMichael P Esch
Jul 17, 2018·The Journal of Chemical Physics·Andrew M SandLaura Gagliardi
Jun 24, 2020·The Journal of Chemical Physics·Chenchen Song, Todd J Martínez
Jan 12, 2019·Annual Review of Physical Chemistry·Benjamin G LevineYinan Shu
Feb 10, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Xueyang LiHongjun Xiang
Feb 10, 2021·Annual Review of Physical Chemistry·Saikat MukherjeeSergey A Varganov
May 17, 2018·Chemical Reviews·Rachel Crespo-Otero, Mario Barbatti
Jan 13, 2018·Journal of the American Chemical Society·Lena SiminePeter J Rossky
Aug 12, 2017·The Journal of Physical Chemistry Letters·Yinan ShuBenjamin G Levine
Aug 9, 2019·Journal of Chemical Theory and Computation·Lan Nguyen TranEric Neuscamman
Oct 8, 2021·Science·E G ChampenoisT J A Wolf

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