Quantum mechanical study of the solvent-dependence of electronic energy transfer rates in a Bodipy closely-spaced dyad
Quantum mechanical study of the solvent-dependence of electronic energy transfer rates in a Bodipy closely-spaced dyad
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Bodipy 紧密排列的二元组中电子能量转移速率的溶剂依赖性的量子力学研究
DOI：
10.1039/c1pp05141e
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发表时间：
2011
影响因子：
3.1
通讯作者：
B. Mennucci
中科院分区：
文献类型：
--
作者：
S. Caprasecca;C. Curutchet;B. Mennucci
从理论上研究了Förster理论描述电子能量传递速率的能力及其与溶剂的依赖关系，在一系列不同极性的15种溶剂中，由两种含硼的二吡咯亚甲基染料组成的刚性紧密排列的二联体，最近由Harriman&Ziessel，Photochem实验研究。光生物醇。SCI。，2010,9960。我们将含时密度泛函理论计算与可极化连续介质模型相结合，分析了该体系的光谱性质和能量传递性质与溶剂的关系。这种方法使我们能够通过在确定分子几何、跃迁密度和电子耦合时始终如一地纳入溶剂效应来检查溶剂对电子因素(溶剂筛选)和结构因素(偶极分离和取向)的影响。此外，我们还分析了桥联作用对染料间电子相互作用的影响。因此，我们能够评估Förster类型的点-偶极近似对于所研究的分子体系是否有效。
The ability of Förster theory to describe electronic energy transfer rates, and their solvent-dependence, have been studied theoretically in a series of 15 solvents of varying degrees of polarity for a rigid closely-spaced dyad, constituted by two boron dipyrromethene dyes, which was recently studied experimentally by Harriman & Ziessel, Photochem. Photobiol. Sci. , 2010, 9, 960. We use time-dependent density functional theory calculations coupled to the polarizable continuum model to analyse the solvent-dependence of the spectroscopic and energy transfer properties of the system. This methodology allows us to examine the impact of the solvent on both electronic (solvent screening) and structural (dipole separation and orientation) factors by consistently incorporating solvent effects in the determination of molecular geometries, transition densities, and electronic couplings. In addition, we analyse the impact of bridge-mediated contributions to the electronic interaction between the dyes. We are therefore able to assess whether a Förster-type point-dipole approximation is valid for the molecular system studied.