TY - JOUR
T1 - Multistate density function theory and the construction of diabatic and adiabatic potential energy surfaces
AU - Qu, Zexing
AU - Gao, Jiali
PY - 2015/11/1
Y1 - 2015/11/1
N2 - A multistate density function theory (MSDFT) based on valence bond theory was introduced. As an application, the MSDFT method was illustrated by the bond dissociation of H2 and the proton transfer between HNO3 and a water molecule. In the dissociation of H2, the MSDFT method yields a correct behavior as the two H atoms stretch to infinity, and gives a potential well in accord with second-order perturbation using complete active space (CASPT2). For the proton transfer process of HNO3, MSDFT can be used to yield both diabatic and adiabatic potential energy curves as a function of the proton transfer reaction coordinate. For the reaction barrier height, the inclusion of an ionic state in a three-state model can significantly improve the accuracy in barrier height in comparison with the high-level results.
AB - A multistate density function theory (MSDFT) based on valence bond theory was introduced. As an application, the MSDFT method was illustrated by the bond dissociation of H2 and the proton transfer between HNO3 and a water molecule. In the dissociation of H2, the MSDFT method yields a correct behavior as the two H atoms stretch to infinity, and gives a potential well in accord with second-order perturbation using complete active space (CASPT2). For the proton transfer process of HNO3, MSDFT can be used to yield both diabatic and adiabatic potential energy curves as a function of the proton transfer reaction coordinate. For the reaction barrier height, the inclusion of an ionic state in a three-state model can significantly improve the accuracy in barrier height in comparison with the high-level results.
KW - Diabatic state
KW - Multistate density function theory
KW - Non-adiabatic coupling
KW - Potential energy surface
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U2 - 10.7503/cjcu20150629
DO - 10.7503/cjcu20150629
M3 - Article
AN - SCOPUS:84949473676
VL - 36
SP - 2236
EP - 2240
JO - Gaodeng Xuexiao Huaxue Xuebao/Chemical Journal of Chinese Universities
JF - Gaodeng Xuexiao Huaxue Xuebao/Chemical Journal of Chinese Universities
SN - 0251-0790
IS - 11
ER -