A state-specific polarizable continuum model time dependent density functional theory method for excited state calculations in solution
A state-specific polarizable continuum model time dependent density functional theory method for excited state calculations in solution
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DOI：
10.1063/1.2222364
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发表时间：
2006-08-07
影响因子：
4.4
通讯作者：
Frisch, Michael J.
中科院分区：
文献类型：
--
作者：
Improta, Roberto;Barone, Vincenzo;Frisch, Michael J.
在所谓的极化连续统模型（PCM）的框架下，建立了一个有效的状态特定（SS）模型，用于在随时间密度泛函理论（TD-DFT）计算激发态中包含溶剂效应。可以处理不同的弛豫时间制度，从而获得许多不同的光谱性质，以及在电子转移过程中最重要的溶剂弛豫能。在两种基准体系（香豆素153和甲醛在不同溶剂中）和偶极溶质嵌入球形腔的极限简单情况下，对SS和传统线性响应（LR）模型进行了比较。结果指出了LR和SS方法的互补性，以及后者模型在极性溶剂方面的优势。PCM-TD-DFT模型在SS和LR变体中的良好标度特性及其在有效量子力学代码中的可用性，为在其自然环境中计算具有技术和/或生物学意义的大分子的可靠光谱特性铺平了道路。(c) 2006年美国物理研究所。
An effective state specific (SS) model for the inclusion of solvent effects in time dependent density functional theory (TD-DFT) computations of excited electronic states has been developed and coded in the framework of the so-called polarizable continuum model (PCM). Different relaxation time regimes can be treated thus giving access to a number of different spectroscopic properties together with solvent relaxation energies of paramount relevance in electron transfer processes. SS and conventional linear response (LR) models have been compared for two benchmark systems (coumarin 153 and formaldehyde in different solvents) and in the limiting simple case of a dipolar solute embedded in a spherical cavity. The results point out the complementarity of LR and SS approaches and the advantages of the latter model especially for polar solvents. The favorable scaling properties of PCM-TD-DFT models in both SS and LR variants and their availability in effective quantum mechanical codes pave the route for the computation of reliable spectroscopic properties of large molecules of technological and/or biological interest in their natural environments. (c) 2006 American Institute of Physics.