TY - JOUR
T1 - The π → π* excited states of long linear polyenes studied by the CASCI-MRMP method
AU - Kurashige, Yuki
AU - Nakano, Haruyuki
AU - Nakao, Yoshihide
AU - Hirao, Kimihiko
N1 - Funding Information:
This research was supported in part by a Grant-in-Aid for Specially Promoted Research, ‘Simulations and Dynamics for Real Systems’, a Grant for the 21st Century COE Program, ‘Human-Friendly Materials based on Chemistry’ from the Ministry of Education, Culture, Sports, Science and Technology of Japan, and by a grant from the Genesis Research Institute.
PY - 2004/12/21
Y1 - 2004/12/21
N2 - Multireference Møller-Plesset perturbation theory with complete active space configuration interaction (CASCI-MRMP) is applied to the study of the valence π → π* excited states of all-trans linear polyenes C 2nH 2n+2 (n = 3-14). Our focus was to determine the nature of the four lowest-lying singlet excited states, 21Ag-,11Bu+,11Bu-and31Ag- and their ordering. The ionic 11Bu+ state is the lowest optically allowed excited state, while the covalent 21Ag-,11Bu-and31Ag- states are the optically forbidden states. Theory predicts that the 11Bu- state becomes lower than the 11Bu+ state at n ≥ 7 and that the 31Ag- state also becomes lower than the 11Bu+ state at n ≥ 11.
AB - Multireference Møller-Plesset perturbation theory with complete active space configuration interaction (CASCI-MRMP) is applied to the study of the valence π → π* excited states of all-trans linear polyenes C 2nH 2n+2 (n = 3-14). Our focus was to determine the nature of the four lowest-lying singlet excited states, 21Ag-,11Bu+,11Bu-and31Ag- and their ordering. The ionic 11Bu+ state is the lowest optically allowed excited state, while the covalent 21Ag-,11Bu-and31Ag- states are the optically forbidden states. Theory predicts that the 11Bu- state becomes lower than the 11Bu+ state at n ≥ 7 and that the 31Ag- state also becomes lower than the 11Bu+ state at n ≥ 11.
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U2 - 10.1016/j.cplett.2004.10.141
DO - 10.1016/j.cplett.2004.10.141
M3 - Article
AN - SCOPUS:10344221009
VL - 400
SP - 425
EP - 429
JO - Chemical Physics Letters
JF - Chemical Physics Letters
SN - 0009-2614
IS - 4-6
ER -