Iozzi Maria Francesca, Mennucci Benedetta, Tomasi Jacopo, Cammi Roberto
Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Italy.
J Chem Phys. 2004 Apr 15;120(15):7029-40. doi: 10.1063/1.1669389.
We present a quantum-mechanical theory to study excitation energy transfers between molecular systems in solution. The model is developed within the time-dependent (TD) density-functional theory and the solvent effects are introduced in terms of the polarizable continuum model (PCM). Unique characteristic of this model is that both "reaction field" and screening effects are included in a coherent and self-consistent way. This is obtained by introducing proper solvent-specific operators in the Kohn-Sham equations and in the corresponding TD scheme. The solvation model exploits the integral equation formalism (IEF) version of PCM and it defines the solvent operators on a molecular cavity modeled on the real three-dimensional (3D) structure of the solute systems. Applications to EET in dimers of ethylene and naphtalene are presented and discussed.
我们提出一种量子力学理论来研究溶液中分子系统间的激发能转移。该模型是在含时密度泛函理论框架下发展起来的，溶剂效应通过极化连续介质模型（PCM）引入。此模型的独特之处在于，“反应场”和屏蔽效应以连贯且自洽的方式被包含在内。这是通过在Kohn-Sham方程及相应的含时方案中引入合适的溶剂特定算符来实现的。溶剂化模型采用PCM的积分方程形式（IEF）版本，并在基于溶质系统真实三维（3D）结构建模的分子腔上定义溶剂算符。文中展示并讨论了该模型在乙烯和萘二聚体的激发能转移中的应用。
