Direct diabatization of electronic states by the fourfold-way: Including dynamical correlation by multi-configuration quasidegenerate perturbation theory with complete active space self-consistent-field diabatic molecular orbitals

Ke R. Yang; Xuefei Xu; Donald G. Truhlar

doi:10.1016/j.cplett.2013.04.036

Direct diabatization of electronic states by the fourfold-way: Including dynamical correlation by multi-configuration quasidegenerate perturbation theory with complete active space self-consistent-field diabatic molecular orbitals

Ke R. Yang, Xuefei Xu, Donald G. Truhlar

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

37 Scopus citations

Abstract

We propose a new scheme for the direct diabatization of MC-QDPT wave functions. Our new scheme utilizes CASSCF diabatic molecular orbitals (DMOs); this is conceptually simpler than the previous approach and can lead to smoother diabatic potentials. We validated the new diabatization scheme, in comparison to CASSCF diabatization and to the original MC-QDPT diabatization scheme, for two test cases, the dissociation of LiF and the reaction of Li + FH → LiF + H. The results with our new scheme suggest that the new scheme with CASSCF DMOs would be a good choice for nonadiabatic dynamics studies in the future.

Original language	English (US)
Pages (from-to)	84-89
Number of pages	6
Journal	Chemical Physics Letters
Volume	573
DOIs	https://doi.org/10.1016/j.cplett.2013.04.036
State	Published - Jun 6 2013

Bibliographical note

Funding Information:
This work was supported in part by the U.S. Department of Energy, Office of Basic Energy Sciences, under SciDAC Grant No. DE-SC0008666 .

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10.1016/j.cplett.2013.04.036

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Direct diabatization of electronic states by the fourfold-way: Including dynamical correlation by multi-configuration quasidegenerate perturbation theory with complete active space self-consistent-field diabatic molecular orbitals. / Yang, Ke R.; Xu, Xuefei; Truhlar, Donald G.
In: Chemical Physics Letters, Vol. 573, 06.06.2013, p. 84-89.

Research output: Contribution to journal › Article › peer-review

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abstract = "We propose a new scheme for the direct diabatization of MC-QDPT wave functions. Our new scheme utilizes CASSCF diabatic molecular orbitals (DMOs); this is conceptually simpler than the previous approach and can lead to smoother diabatic potentials. We validated the new diabatization scheme, in comparison to CASSCF diabatization and to the original MC-QDPT diabatization scheme, for two test cases, the dissociation of LiF and the reaction of Li + FH → LiF + H. The results with our new scheme suggest that the new scheme with CASSCF DMOs would be a good choice for nonadiabatic dynamics studies in the future.",

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T2 - Including dynamical correlation by multi-configuration quasidegenerate perturbation theory with complete active space self-consistent-field diabatic molecular orbitals

AU - Yang, Ke R.

AU - Xu, Xuefei

AU - Truhlar, Donald G.

N1 - Funding Information: This work was supported in part by the U.S. Department of Energy, Office of Basic Energy Sciences, under SciDAC Grant No. DE-SC0008666 .

PY - 2013/6/6

Y1 - 2013/6/6

N2 - We propose a new scheme for the direct diabatization of MC-QDPT wave functions. Our new scheme utilizes CASSCF diabatic molecular orbitals (DMOs); this is conceptually simpler than the previous approach and can lead to smoother diabatic potentials. We validated the new diabatization scheme, in comparison to CASSCF diabatization and to the original MC-QDPT diabatization scheme, for two test cases, the dissociation of LiF and the reaction of Li + FH → LiF + H. The results with our new scheme suggest that the new scheme with CASSCF DMOs would be a good choice for nonadiabatic dynamics studies in the future.

AB - We propose a new scheme for the direct diabatization of MC-QDPT wave functions. Our new scheme utilizes CASSCF diabatic molecular orbitals (DMOs); this is conceptually simpler than the previous approach and can lead to smoother diabatic potentials. We validated the new diabatization scheme, in comparison to CASSCF diabatization and to the original MC-QDPT diabatization scheme, for two test cases, the dissociation of LiF and the reaction of Li + FH → LiF + H. The results with our new scheme suggest that the new scheme with CASSCF DMOs would be a good choice for nonadiabatic dynamics studies in the future.

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Direct diabatization of electronic states by the fourfold-way: Including dynamical correlation by multi-configuration quasidegenerate perturbation theory with complete active space self-consistent-field diabatic molecular orbitals

Abstract

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