TY - JOUR
T1 - A theoretical study of cyclohexadiene/hexatriene photochemical interconversion
T2 - Multireference configuration interaction potential energy surfaces and transition probabilities for the radiationless decays
AU - Tamura, Hiroyuki
AU - Nanbu, Shinkoh
AU - Nakamura, Hiroki
AU - Ishida, Toshimasa
N1 - Funding Information:
This study was supported by a Grant-in-Aid for Specially Promoted Research on ‘studies of non-adiabatic chemical dynamics based on the Zhu–Nakamura theory’ from MEXT, Japan.
PY - 2005/1/11
Y1 - 2005/1/11
N2 - The overall energetics and the feature of reactive potential energy surfaces for the photochemical interconversion between cyclohexadiene (CHD) and all-cis-hexatriene (cZc-HT) have been investigated using the multireference configuration interaction (MRCI) calculations. The adiabatic and the diabatic potential energy surfaces of the ground and the excited states have been calculated along the Jacobi coordinates. The conical intersections among the states are estimated and the corresponding non-adiabatic transition probabilities are calculated using the semiclassical Zhu-Nakamura formula. The 1 1B-2 1A decay occurs by C 2-symmetry-breaking motion around the conical intersection. The non-adiabatic transition to 1 1A occurs by the motion toward the 5-membered ring.
AB - The overall energetics and the feature of reactive potential energy surfaces for the photochemical interconversion between cyclohexadiene (CHD) and all-cis-hexatriene (cZc-HT) have been investigated using the multireference configuration interaction (MRCI) calculations. The adiabatic and the diabatic potential energy surfaces of the ground and the excited states have been calculated along the Jacobi coordinates. The conical intersections among the states are estimated and the corresponding non-adiabatic transition probabilities are calculated using the semiclassical Zhu-Nakamura formula. The 1 1B-2 1A decay occurs by C 2-symmetry-breaking motion around the conical intersection. The non-adiabatic transition to 1 1A occurs by the motion toward the 5-membered ring.
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U2 - 10.1016/j.cplett.2004.11.111
DO - 10.1016/j.cplett.2004.11.111
M3 - Article
AN - SCOPUS:11144307435
VL - 401
SP - 487
EP - 491
JO - Chemical Physics Letters
JF - Chemical Physics Letters
SN - 0009-2614
IS - 4-6
ER -