TY - JOUR
T1 - Direct diabatization of electronic states by the fourfold-way
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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U2 - 10.1016/j.cplett.2013.04.036
DO - 10.1016/j.cplett.2013.04.036
M3 - Article
AN - SCOPUS:84878228163
SN - 0009-2614
VL - 573
SP - 84
EP - 89
JO - Chemical Physics Letters
JF - Chemical Physics Letters
ER -