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dc.contributor.authorGan, Yanzhenen_US
dc.contributor.authorYue, Lingen_US
dc.contributor.authorGuo, Xugengen_US
dc.contributor.authorZhu, Chaoyuanen_US
dc.contributor.authorCao, Zexingen_US
dc.date.accessioned2018-08-21T05:54:03Z-
dc.date.available2018-08-21T05:54:03Z-
dc.date.issued2017-05-21en_US
dc.identifier.issn1463-9076en_US
dc.identifier.urihttp://dx.doi.org/10.1039/c6cp08929aen_US
dc.identifier.urihttp://hdl.handle.net/11536/145529-
dc.description.abstractAn on-the-fly trajectory surface hopping dynamic simulation has been performed for revealing the multi-state nonadiabatic deactivation mechanism of coumarin. The mechanism involves three adiabatic excited states, S-3(pi pi* L-b), S-2(n pi*, pi pi* L-a) and S-1(pi pi* L-a, n pi*), and the ground state S-0 at the four stateaveraged complete active space self-consistent field, SA(4)-CASSCF(12,10)/6-31G* level of theory. Upon photoexcitation to the third excited state S-3(pi pi* L-b) in the Franck-Condon region, 80% sampling trajectories decay to the dark S-2(n pi*) state within an average of 5 fs via the conical intersection S-3(pi pi* L-b)/S-2(n pi*), while 20% decay to the S-2(pi pi* L-a) state within an average of 11 fs via the conical intersection S3(pi pi* L-b)/S-2(pi pi* L-a). Then, sampling trajectories via S-2(n pi*)/S-1(pi pi* L-a) continue with ultrafast decay processes to give a final distribution of quantum yields as follows: 42% stay on the dark S-1(n pi*) state, 43.3% go back to the ground S-0 state, 12% undergo a ring-opening reaction to the Z-form S-0(Z) state, and 2.7% go to the E-form S-0(E) state. The lifetimes of the excited states are estimated as follows: the S-3 state is about 12 fs on average, the S-2 state is about 80 fs, and the S-1 state has a fast component of about 160 fs and a slow component of 15 ps. The simulated ultrafast radiationless deactivation pathways of photoexcited coumarin immediately interpret the experimentally observed weak fluorescence emission.en_US
dc.language.isoen_USen_US
dc.titleMulti-state nonadiabatic deactivation mechanism of coumarin revealed by ab initio on-the-fly trajectory surface hopping dynamic simulationen_US
dc.typeArticleen_US
dc.identifier.doi10.1039/c6cp08929aen_US
dc.identifier.journalPHYSICAL CHEMISTRY CHEMICAL PHYSICSen_US
dc.citation.volume19en_US
dc.citation.spage12094en_US
dc.citation.epage12106en_US
dc.contributor.department應用化學系分子科學碩博班zh_TW
dc.contributor.departmentInstitute of Molecular scienceen_US
dc.identifier.wosnumberWOS:000401640600038en_US
Appears in Collections:Articles