Piserchia Andrea, Banerjee Shiladitya, Barone Vincenzo
Scuola Normale Superiore , piazza dei Cavalieri 7, I-56126 Pisa, Italy.
J Chem Theory Comput. 2017 Dec 12;13(12):5900-5910. doi: 10.1021/acs.jctc.7b00685. Epub 2017 Nov 13.
A new and more general approach to diffusion problems with the inclusion of reactivity among different coupled diffusional states is rationalized and presented. The integration of our previous developments in such a field [Phys. Chem. Chem. Phys., 2015, 17, 17362-17374; J. Chem. Theory Comput., 2016, 12, 3482-3490] are implemented in a software package tool allowing the generic user to set up and run diffusional calculations with very low efforts. We show the applicability of the whole framework to a generic diffusional case of chemical interest that is the study case of (N,N-dimethylamino)benzonitrile (DMABN) fluorescence, whose excited state undergoes twisted intramolecular charge transfer (TICT) relaxation. The population dynamics of the excited state coupled to the ground state is followed, and a fluorescence decay spectrum is calculated. The theoretical and numerical background here presented is robust and general enough to complement a wide number of diffusional problems of current interest.
一种新的、更通用的处理扩散问题的方法被合理化并呈现出来，该方法考虑了不同耦合扩散状态之间的反应性。我们之前在该领域的研究成果[《物理化学化学物理》，2015年，17卷，17362 - 17374页；《化学理论与计算杂志》，2016年，12卷，3482 - 3490页]被整合到一个软件包工具中，使得普通用户能够轻松地设置和运行扩散计算。我们展示了整个框架在一个具有化学意义的通用扩散案例中的适用性，该案例是对（N，N - 二甲基氨基）苯甲腈（DMABN）荧光的研究，其激发态经历扭曲分子内电荷转移（TICT）弛豫。跟踪了与基态耦合的激发态的布居动力学，并计算了荧光衰减光谱。这里给出的理论和数值背景足够稳健和通用，足以补充当前许多感兴趣的扩散问题。
