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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Reliable Predictions of Benzophenone Singlet–Triplet Transition Rates: A Second-Order Cumulant Approach
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Reliable Predictions of Benzophenone Singlet–Triplet Transition Rates: A Second-Order Cumulant Approach

机译：二苯甲酮态三重态转换率的可靠预测：二阶累积方法

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摘要

Fermi golden rule and second-order cumulant expansion of the time-dependent density matrix have been used to compute from first principles the rate of intersystem crossing in benzophenone, using minimum-energy geometries and normal modes of vibrations computed at the TDDFT/CAM-B3LYP level. Both approaches yield reliable values of the S_(1) decay rate, the latter being almost in quantitative agreement with the results of time-dependent spectroscopic measurements (0.154 ps~(–1) observed vs 0.25 ps~(–1) predicted). The Fermi golden rule slightly overestimates the decay rate of S_(1) state (k _(d) = 0.45 ps~(–1)) but provides better insights into the chemico-physical parameters, which govern the transition from a thermally equilibrated population of S_(1), showing that the indirect mechanism is much faster than the direct one because of the vanishingly small Franck–Condon weighted density of states at ΔE of transition.
机译：费米黄金法则和含时密度矩阵的二阶累积量展开式已用于从第一原理计算二苯甲酮的系统间交叉速率，使用在TDDFT/CAM-B3LYP水平上计算的最小能量几何和正常振动模式。这两种方法都产生了可靠的S_1衰变率值，后者几乎与随时间变化的光谱测量结果（观察到的0.154 ps~（-1）与预测的0.25 ps~（-1））在数量上一致。费米黄金法则略微高估了S_1态的衰变速率（k_1（d）=0.45 ps~（-1）），但对化学物理参数提供了更好的见解，这些参数控制着S_1的热平衡布居的转变，表明间接机制比直接机制快得多，因为在ΔE跃迁处的态密度非常小。

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