Indian Institute of Science Education and Research, Thiruvananthapuram, Maruthamala PO,Vithura, Thiruvananthapuram 695551, India.
WPI-Research Initiative-Institute of Transformative Bio-Molecules, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
J Chem Phys. 2019 Dec 7;151(21):214304. doi: 10.1063/1.5127271.
The excited-state intramolecular proton transfer process in 3-hydroxyflavone is investigated based on the computed structural parameters and energetics of stationary points of vibronically coupled S-S potential energy surfaces. A conical intersection close to the Franck-Condon point on S is identified. The minimum energy of the conical intersection is found to be near-degenerate with the equilibrium minimum of S. Quantum nuclear wavepacket simulations revealed a small population transfer from the "bright" S to "dark" S on a time scale shorter than the O-H stretching vibrational period. Such a nonadiabatic transition opens up the possibility of new photophysical and photochemical pathways, including the proton transfer via S.
基于计算得到的 3-羟基黄酮分子的激发态内质子转移过程，研究了振动耦合 S-S 势能表面上的定态点的结构参数和能量。在 S 上，我们确定了一个接近 Franck-Condon 点的锥形交叉点。发现该交叉点的最低能量与 S 的平衡最小值近简并。量子核波包模拟显示，在 O-H 伸缩振动周期内，“亮”S 到“暗”S 的小部分电子转移。这种非绝热跃迁为新的光物理和光化学途径开辟了可能性，包括通过 S 的质子转移。
