Energy transfer dynamics and kinetics of elementary processes (promoted) by gas‐phase CO2‐N2 collisions: Selectivity control by the anisotropy of the interaction
Energy transfer dynamics and kinetics of elementary processes (promoted) by gas‐phase CO2‐N2 collisions: Selectivity control by the anisotropy of the interaction
复制标题
气相 CO2-N2 碰撞（促进）的能量传递动力学和基本过程动力学：相互作用各向异性的选择性控制
DOI：
10.1002/jcc.24359
复制
发表时间：
2016
影响因子：
3
通讯作者：
M. Bartolomei
中科院分区：
文献类型：
--
作者：
A. Lombardi;F. Pirani;A. Laganà;M. Bartolomei
在这项工作中，我们利用了一种新的配方的势能和相关的计算程序，它体现了内部和分子间的组件之间的耦合，表征可能的倾向的碰撞动力学的能量转移过程中的兴趣模拟和控制的现象发生在各种平衡和非平衡环境。本文的研究重点是原型CO2-N2系统，其相互作用的分子内组分是根据多体膨胀建模的，而分子间组分是根据最近开发的键相互作用分子中心方法建模的。势能面的这种公式化的主要优点是（a）真正全维（即，明确地考虑了与单体的几何和电子结构上的分子振动和旋转相关的坐标的所有变化，而没有冻结任何键或角），（B）比相互作用的其它常用公式更灵活，和（c）非常适合于拟合程序，更好地坚持精确的从头算数据，并且对实验排列依赖的信息敏感。特别注意的事实是，振动和旋转能量的变化有更高的（定性和定量）的能量转移的影响时，采用更准确的配方的分子间相互作用（相对于使用刚性单体时获得的）。这使得势能面更适合于等离子体，燃烧和大气化学计算应用中的气体混合物的动力学建模。© 2016 Wiley Periodicals，Inc.
In this work, we exploit a new formulation of the potential energy and of the related computational procedures, which embodies the coupling between the intra and intermolecular components, to characterize possible propensities of the collision dynamics in energy transfer processes of interest for simulation and control of phenomena occurring in a variety of equilibrium and nonequilibrium environments. The investigation reported in the paper focuses on the prototype CO2–N2 system, whose intramolecular component of the interaction is modeled in terms of a many body expansion while the intermolecular component is modeled in terms of a recently developed bonds‐as‐interacting‐molecular‐centers' approach. The main advantage of this formulation of the potential energy surface is that of being (a) truly full dimensional (i.e., all the variations of the coordinates associated with the molecular vibrations and rotations on the geometrical and electronic structure of the monomers, are explicitly taken into account without freezing any bonds or angles), (b) more flexible than other usual formulations of the interaction and (c) well suited for fitting procedures better adhering to accurate ab initio data and sensitive to experimental arrangement dependent information. Specific attention has been given to the fact that a variation of vibrational and rotational energy has a higher (both qualitative and quantitative) impact on the energy transfer when a more accurate formulation of the intermolecular interaction (with respect to that obtained when using rigid monomers) is adopted. This makes the potential energy surface better suited for the kinetic modeling of gaseous mixtures in plasma, combustion and atmospheric chemistry computational applications. © 2016 Wiley Periodicals, Inc.