Abstract
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.
| Original language | English |
|---|---|
| Pages (from-to) | 425-429 |
| Number of pages | 5 |
| Journal | Chemical Physics Letters |
| Volume | 400 |
| Issue number | 4-6 |
| DOIs | |
| Publication status | Published - Dec 21 2004 |
All Science Journal Classification (ASJC) codes
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry
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Kurashige, Y., Nakano, H., Nakao, Y., & Hirao, K. (2004). The π → π* excited states of long linear polyenes studied by the CASCI-MRMP method. Chemical Physics Letters, 400(4-6), 425-429. https://doi.org/10.1016/j.cplett.2004.10.141