A computational approach for modeling and predicting triplet energy sensitization of organic molecules is described, which involves sampling the instantaneous, vertical energy gaps over molecular vibrational motions. This approach provides new theoretical support for the hot-band mechanism of energy transfer, in which the energy difference between donor and acceptor can be lessened by geometric distortions. We demonstrate excellent predictive performance against experimental triplet energies, with R2 = 0.97 and a mean absolute error (MAE) of 1.7 kcal/mol, for a collection of 24 small organic molecules, whereas a static, adiabatic description performs significantly worse (R2 = 0.51, MAE = 9.5 kcal/mol). Using this approach, it is possible to quantitatively predict the correct E/Z-isomerism of alkenes under energy transfer, for which adiabatic calculations predict the wrong outcome.

中文翻译：

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动态垂直三重态能量：了解和预测三重态能量转移


描述了一种用于建模和预测有机分子三重态能量敏化的计算方法，该方法涉及对分子振动运动中的瞬时垂直能隙进行采样。该方法为能量转移的热带机制提供了新的理论支持，其中供体和受体之间的能量差异可以通过几何畸变来减小。对于一组 24 个有机小分子，我们展示了对实验三重态能量的出色预测性能，R2 = 0.97，平均绝对误差 （MAE） 为 1.7 kcal/mol，而静态、绝热描述的性能明显更差（R2 = 0.51，MAE = 9.5 kcal/mol）。使用这种方法，可以定量预测能量传递下烯烃的正确 E/Z 异构体，而绝热计算会预测错误的结果。