A straightforward analytical model for an approximate estimate of the energy disposal into the vibrational degrees of freedom of molecules formed by a bimolecular chemical reaction with the minimum required data (energy barriers in both directions and molecular properties of the products and reagents, such as numbers of internal degrees of freedom, atomic compositions, static polarizabilities, and vibrational frequencies) is proposed. This model is theoretically grounded, and the known regularities in energy disposal in chemical reactions are properly taken into account. To adjust it, reliable previous data (of both experimental and theoretical origin) on the fraction of the available chemical energy released into vibrations for a large body of bimolecular reactions of various types are utilized. For some elementary processes (in total, 25 reactions) our results of post-transition state molecular dynamics simulations are additionally engaged. In this connection, the possibility of using the single trajectory approach for predicting the energy deposition in the vibrational degrees of freedom of molecules is validated. We show that the accuracy of the developed model is reasonable in view of the significant uncertainties in the reference data and is enough for many practical applications where the thermodynamic nonequilibrium between internal and translational degrees of freedom of molecules is essential and there is a need for express assessments of the fraction of energy going into vibrations for multiple elementary reactions.

一个简单的分析模型，可以用最小的所需数据（在产品和试剂的方向和分子特性的双向能量壁垒，例如分子数目）对由双分子化学反应形成的分子的振动自由度中的能量处置进行近似估计。内部自由度，原子组成，静态极化率和振动频率）。该模型从理论上讲是扎根的，并且适当考虑了化学反应中已知的能量处置规律。为了对其进行调整，利用了关于各种类型的大分子双分子反应释放到振动中的可用化学能的分数的可靠的先前数据（来自实验和理论）。对于某些基本流程（总计，25个反应），我们的过渡后状态分子动力学模拟的结果是另外参与。在这方面，证实了使用单轨迹方法来预测分子的振动自由度中的能量沉积的可能性。我们表明，鉴于参考数据中的重大不确定性，开发模型的准确性是合理的，并且对于分子的内部和平移自由度之间的热力学非平衡至关重要且需要表达的许多实际应用而言已足够评估振动对多个基本反应的能量分数。验证了使用单轨迹方法预测分子在振动自由度上的能量沉积的可能性。我们表明，鉴于参考数据中的重大不确定性，开发模型的准确性是合理的，并且对于分子的内部和平移自由度之间的热力学非平衡至关重要且需要表达的许多实际应用而言已足够评估振动对多个基本反应的能量分数。验证了使用单轨迹方法预测分子在振动自由度上的能量沉积的可能性。我们表明，鉴于参考数据中的重大不确定性，开发模型的准确性是合理的，并且对于分子的内部和平移自由度之间的热力学非平衡至关重要且需要表达的许多实际应用而言已足够评估振动对多个基本反应的能量分数。