Mode specificity in the unimolecular dissociation of formaldehyde (H2CO→H2+CO), a two‐mode model
Mode specificity in the unimolecular dissociation of formaldehyde (H2CO→H2+CO), a two‐mode model
复制标题
甲醛单分子解离 (H2CO→H2+CO) 的模式特异性，双模式模型
DOI：
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发表时间：
1983
期刊：
影响因子：
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通讯作者：
W. Miller
中科院分区：
文献类型：
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作者：
B. A. Waite;S. Gray;W. Miller
反应路径（质量加权笛卡尔坐标系中的最小能量路径）和所有耦合函数完全表征了米勒、汉迪和亚当斯[J. Chem. Phys. 72，99（1980）]的反应路径哈密顿量，已经计算了甲醛在其基态电子状态下的单分子解离（H2 CO →H2+CO）。反应坐标和其他四个面内振动模式彼此强烈耦合，但面外振动仅直接耦合到反应坐标。Waite和米勒[J. Chem. Phys. 73，3713（1980）; 74，3910（1981）]对状态特异性单分子速率常数的计算是针对由反应坐标和面外振动组成的双模模型进行的，并且观察到显著程度的模式特异性;即，给定亚稳态的单分子速率常数不是该状态能量的平滑函数。这表明，这种模式的特异性可能会持续…
The reaction path (the minimum energy path in mass‐weighted Cartesian coordinates) and all the coupling functions which fully characterize the reaction path Hamiltonian of Miller, Handy, and Adams [J. Chem. Phys. 72, 99 (1980)], have been calculated for the unimolecular dissociation of formaldehyde (H2CO→H2+CO) in its ground electronic state. The reaction coordinate and the four other in‐plane vibrational modes are strongly coupled to each other, but the out‐of‐plane vibration is coupled directly only to the reaction coordinate. Calculations of the type of Waite and Miller [J. Chem. Phys. 73, 3713 (1980); 74, 3910 (1981)] for the state‐specific unimolecular rate constants are carried out for a two‐mode model consisting of the reaction coordinate and the out‐of‐plane vibration, and one observes a significant degree of mode specificity; i.e., the unimolecular rate constant for a given metastable state is not a smooth function of the energy of the state. It is suggested that this mode specificity may persist...