Farmani Maryam, Park Woojin, Lee Seunghoon, Choi Cheol Ho
Department of Chemistry, Kyungpook National University, Daegu, 41566, South Korea.
Department of Chemistry, Seoul National University, Seoul, 151-747, South Korea.
Photochem Photobiol Sci. 2025 May 24. doi: 10.1007/s43630-025-00737-4.
Multi-state nonadiabatic molecular dynamics simulations combined with MRSF-TDDFT have revealed that the quantum yield of photoproducts in cis-stilbene is dependent on the initial temperature of the ground state, thereby resolving controversies regarding the competition between isomerization and ring-closure reactions. Specifically, 4,4-dihydrophenanthrene (DHP) is preferentially formed at low temperatures, while trans-stilbene is favored at high temperatures. The ethylenic torsional motions ( ) are particularly coupled with the initial thermal condition, tipping the balance of the competition.
结合MRSF-TDDFT的多态非绝热分子动力学模拟表明，顺式芪中光产物的量子产率取决于基态的初始温度，从而解决了关于异构化和闭环反应之间竞争的争议。具体而言，4,4-二氢菲（DHP）在低温下优先形成，而反式芪在高温下更易形成。烯键扭转运动（ ）与初始热条件特别相关，从而打破了竞争的平衡。
