Department of Chemistry, Northwestern University, Evanston, Illinois 60208, USA.
J Phys Chem A. 2010 Aug 26;114(33):8665-75. doi: 10.1021/jp101235a.
We model the triplet-triplet energy-transfer experiments from the Closs group [ Closs , G. L. ; et al. J. Am. Chem. Soc. 1988 , 110 , 2652. ] using a combination of Marcus theory and either Boys or Edmiston-Ruedenberg localized diabatization, and we show that relative and absolute rates of electronic excitation transfer may be computed successfully. For the case where both the donor and acceptor occupy equatorial positions on a rigid cyclohexane bridge, we find beta(calc) = 2.8 per C-C bond, compared with the experimental value beta(exp) = 2.6. This work highlights the power of using localized diabatization methods as a tool for modeling nonequilibrium processes.
我们使用 Marcus 理论和 Boys 或 Edmiston-Ruedenberg 局域化二能级化方法对来自 Closs 小组[Closs, G. L. ; 等人。美国化学学会 1988 年，110,2652。]的三重态-三重态能量转移实验进行建模，我们表明可以成功计算电子激发转移的相对和绝对速率。对于供体和受体都占据刚性环己烷桥的赤道位置的情况，我们发现β(calc) = 2.8 每 C-C 键，而实验值β(exp) = 2.6。这项工作强调了使用局域化二能级化方法作为模拟非平衡过程的工具的强大功能。
