Vibrational energy transfer in molecular collisions: An information theoretic analysis and synthesis
Vibrational energy transfer in molecular collisions: An information theoretic analysis and synthesis
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分子碰撞中的振动能量转移：信息论分析与综合
DOI：
10.1063/1.431197
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发表时间：
1975
影响因子：
4.4
通讯作者：
R. Levine
中科院分区：
文献类型：
--
作者：
I. Procaccia;R. Levine
振动能量转移的状态到状态速率常数（V-V和V-T）使用“指数间隙”表示来表征。碰撞分析包括V-T和V-V转移率的实验结果，V-T转移率的轨迹计算（通过非弹性和反应，原子交换，碰撞）和V-V转移率的量子计算。分析结果的术语是实际比率与先前（或参考）比率的偏差。先验率是在假设（在给定的碰撞能量下）所有的最终状态都是同样可能的基础上计算的。对于几乎所有的情况下，可以用一个单一的参数来表征的神经元。这个参数的大小（及其温度依赖性）可以预测使用批量平均值。这样的预测证明实验和轨迹计算率。微观动力学和宏观动力学之间的联系是由使用锻造…
State‐to‐state rate constants for vibrational energy transfer (both V–V and V–T) are characterized using an ’’exponential gap’’ representation. The collisions analyzed include experimental results for both V–T and V–V transfer rates, trajectory computations for V–T transfer rates (via both inelastic and reactive, atom exchange, collisions) and quantal computations for V–V transfer rates. The results are analyzed in terms of the surprisal, a measure of deviation of the actual rate from the prior (or reference) rate. The prior rates are computed on the basis of the assumption that (at a given collision energy) all final states are equally probable. For almost all cases the surprisal could be characterized by a single parameter. The magnitude of this parameter (and its temperature dependence) could be predicted using bulk averages only. Such predictions are demonstrated for both experimental and trajectory computed rates. The link between the microscopic dynamics and macroscopic kinetics is forged by the use...