Chimie et Interdisciplinarité, Synthèse, Analyse, Modélisation (CEISAM), UMR CNRS no. 6230, BP 92208, Université de Nantes, 2, Rue de la Houssinière, 44322 Nantes Cedex 3, France.
Phys Chem Chem Phys. 2011 Oct 14;13(38):16987-98. doi: 10.1039/c1cp22144b. Epub 2011 Aug 31.
In this perspective, we present an overview of recent progress on Time-Dependent Density Functional Theory (TD-DFT) with a specific focus on its accuracy and on models able to take into account environmental effects, including complex media. To this end, we first summarise recent benchmarks and define an average TD-DFT accuracy in reproducing excitation energies when a conventional approach is used. Next, coupling of TD-DFT with models able to account for different kinds of interactions between a central chromophore and nearby chemical objects (solvent, organic cage, metal as well as semi-conducting surface) is investigated. Examples of application to excitation properties are presented, allowing to briefly describe several recent computational strategies. In addition, an extension of TD-DFT to describe a phenomenon involving interacting chromophores, e.g. the electronic energy transfer (EET), is presented to illustrate that this methodology can be applied to processes beyond the vertical excitation. This perspective therefore aims to provide to non-specialists a flavour of recent trends in the field of simulations of excited states in "realistic" situations.
在这篇观点文章中，我们概述了时变密度泛函理论（TD-DFT）的最新进展，特别关注其准确性和能够考虑环境效应的模型，包括复杂介质。为此，我们首先总结了最近的基准测试，并定义了在使用传统方法时，重现激发能的平均 TD-DFT 精度。接下来，研究了将 TD-DFT 与能够解释中心发色团与附近化学物体（溶剂、有机笼、金属以及半导体表面）之间不同相互作用的模型进行耦合。介绍了应用于激发性质的示例，允许简要描述几种最近的计算策略。此外，还提出了将 TD-DFT 扩展到描述涉及相互作用发色团的现象，例如电子能量转移（EET），以说明该方法可应用于超出垂直激发的过程。因此，本观点旨在为非专业人士提供在“真实”情况下模拟激发态领域的最新趋势的简介。
