標題: Quantum yields of singlet and triplet chemiexcitation of dimethyl 1,2-dioxetane: ab initio nonadiabatic molecular dynamic simulations
作者: Yue, Ling
Yu, Le
Xu, Chao
Zhu, Chaoyuan
Liu, Yajun
交大名義發表
應用化學系
應用化學系分子科學碩博班
National Chiao Tung University
Department of Applied Chemistry
Institute of Molecular science
公開日期: 28-五月-2020
摘要: The global nonadiabatic switching on-the-fly trajectory surface hopping simulation at the 8SA-CASSCF quantum level has been performed to estimate the quantum yield of chemiexcitation for the uncatalyzed decomposition reaction of the open-shell biradical trans-3,4-dimethyl-1,2-dioxetane system. The present ab initio nonadiabatic molecular dynamic simulation involving both conical intersection and intersystem crossing is to compute for the first time the population evolution of quantum yields at the four lowest singlet and four lowest triplet states. The simulated results demonstrate not only the stepwise dissociation of O-O and C-C bond breaking, but also confirm the existence of a biradical entropic trap which is responsible for chemiexcitation. The simulated quantum yield of the triplet chemiexcitation phi(T1) = 0.266 +/- 0.096 agrees with the experimental value of 0.20 +/- 0.04 very well. The present nonadiabatic molecular dynamic simulation of dimethyl 1,2-dioxetanes provides a further advanced understanding and stepping stone for future studies on chemi- and bio-luminescence.
URI: http://dx.doi.org/10.1039/d0cp00811g
http://hdl.handle.net/11536/154495
ISSN: 1463-9076
DOI: 10.1039/d0cp00811g
期刊: PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume: 22
Issue: 20
起始頁: 11440
結束頁: 11451
顯示於類別:期刊論文