Garcia Ernesto, Pirani Fernando, Laganà Antonio, Martí Carles
Departamento de Quimica Fisica, Universidad del Pais Vasco (UPV/EHU), 01006 Vitoria, Spain.
Phys Chem Chem Phys. 2017 May 10;19(18):11206-11211. doi: 10.1039/c7cp01340j.
In the study of non-reactive energy transfer between O and N molecules bearing different vibrationally excited states we have faced the problem of selecting a proper formulation of the interaction. To this end we have compared the values of the related observables computed either on a potential energy surface globally fitted to very large ab initio potential energy values [Varga et al., J. Chem. Phys., 2016, 144, 024310] or on two more traditional ones formulated as a combination of an intra- and inter-molecular model component of the interaction (and based on a different combined use of experimental and ab initio information) [Garcia et al., J. Phys. Chem. A, 2016, 120, 5208] in order to enforce an appropriate modelling of the long-range tail of the potential, crucial for the description of inelastic vibrational energy transfer. A detailed graphical analysis of the potential plus a quantitative analysis of the computed opacity functions, of the state-to-state rate coefficients, of the second virial coefficient and of the integral non-reactive cross section allowed us to conclude that the model formulation of the interaction has to be preferred for non-reactive studies of the O + N energy transfer processes in thermal and subthermal regimes.
在对处于不同振动激发态的O分子和N分子之间的非反应能量转移的研究中，我们面临着选择合适的相互作用公式的问题。为此，我们比较了在全局拟合到非常大的从头算势能值的势能面上计算得到的相关可观测量的值[瓦尔加等人，《化学物理杂志》，2016年，144卷，024310]，以及在另外两个更传统的势能面上计算得到的相关可观测量的值，这两个势能面是由相互作用的分子内和分子间模型分量组合而成（并基于实验和从头算信息的不同组合使用）[加西亚等人，《物理化学杂志A》，2016年，120卷，5208]，以便对势能的长程尾部进行适当建模，这对于描述非弹性振动能量转移至关重要。对势能进行详细的图形分析，并对计算得到的不透明度函数、态到态速率系数、第二维里系数和积分非反应截面进行定量分析，使我们能够得出结论，对于热态和亚热态下O + N能量转移过程的非反应研究，必须优先选择相互作用的模型公式。
