Random coupling model for molecular dissociation
Random coupling model for molecular dissociation
复制标题
分子解离的随机耦合模型
DOI：
10.1063/1.1682039
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发表时间：
1974
影响因子：
4.4
通讯作者：
S. Rice
中科院分区：
文献类型：
--
作者：
E. Heller;S. Rice
本文提出并求解了Rice-McLaughlin-Jortner（RMJ）型分子解离的序贯耦合模型，其中通常的状态间恒定耦合的假设被随机耦合的假设所取代.之前发现的常数耦合的反直观的非顺序分支行为被消除，我们发现完全顺序的时间依赖性服从唯象速率方程。我们隔离的特点，常数与随机耦合，引起的分支与顺序的行为，在简单的物理模型和波函数的相干性的考虑。它的结论是，恒定耦合是不合适的大多数分子，和随机耦合假设的效果验证使用的随机相位近似，这反过来又导致分子衰减，如果每个quasibound分子水平耦合到自己的连续。我们的结论不会改变，当我们解决了一个外部的问题。
In this paper, we propose and solve sequential coupling models for molecular dissociation of the Rice‐McLaughlin‐Jortner (RMJ) type in which the usual assumption of constant coupling among the states is replaced by an assumption of random coupling. The counter‐intuitive nonsequential branching behavior found previously for constant coupling is eliminated and we find completely sequential time dependence which obeys the phenomenological rate equations. We isolate the features of constant vs random coupling which give rise to the branching vs sequential behavior in terms of simple physical models and considerations of the coherence properties of the wavefunction. It is concluded that constant coupling is inappropriate for most molecules, and that the random coupling assumption has the effect of validating the use of a random phase approximation which in turn causes the molecule to decay as if each quasibound molecular level is coupled to its own continuum. Our conclusions do not change when we solve an exte...