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Three-Dimensional Master Equation (3DME) Approach
The Journal of Physical Chemistry A ( IF 2.9 ) Pub Date : 2018-09-04 00:00:00 , DOI: 10.1021/acs.jpca.8b06593
Thanh Lam Nguyen 1 , John F. Stanton 1
Affiliation  

The master equation technique is a standard tool to interpret gas-phase experimental kinetic results as well as to provide phenomenological rate coefficients for modeling. When there are significant changes of rotational constants along the reaction coordinate from a reactant through a transition state (TS) to product(s), including effects of angular momentum explicitly in a master equation model becomes vitally important. In this work, assuming that the K quantum number is adiabatic for both the TS and reactant, we developed an algorithm for pragmatic solutions of a three-dimensional master equation (3DME) that involves internal energy, total angular momentum (J), and its projection K. Two examples (one is for a thermally activated isomerization of CH3NC to CH3CN via a tight TS, and the other is for a thermally activated dissociation of NH3 to H + NH2 via a loose, variational TS) are given. In addition, comparison of 3DME results with experiment as well as with those of 1DME and 2DME are documented.

中文翻译:

三维主方程(3DME)方法

主方程技术是解释气相实验动力学结果以及为建模提供现象学速率系数的标准工具。当从反应物到过渡态(TS)到反应产物的沿着反应坐标的旋转常数发生重大变化时,在主方程模型中明确包括角动量的影响就变得至关重要。在这项工作中,假设K量子数对于TS和反应物都是绝热的,我们开发了一种用于求解包含内部能,总角动量(J)及其维数的三维主方程(3DME)的务实解决方案的算法。投影ķ。两个例子(一个用于CH的热活化异构化图3给出了通过紧密TS将NC 3转化为CH 3 CN的方法,另一个是通过松散的变体TS将NH 3热活化解离为H + NH 2。此外,还记录了3DME结果与实验以及1DME和2DME结果的比较。
更新日期:2018-09-04
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