Andrienko Daniil A
Department of Aerospace Engineering, Texas A&M University, H. R. Bright Building, 701 Ross Street, College Station, Texas 77840, USA.
J Chem Phys. 2020 Jan 31;152(4):044305. doi: 10.1063/1.5142191.
The mechanism of vibrational relaxation and dissociation in the O-O system at elevated temperatures is investigated by means of molecular dynamics. The most recent O potential energy surfaces (PESs), obtained from the first principles quantum mechanical calculations [Varga et al., J. Chem. Phys. 147, 154312 (2017)], are used to derive a complete set of state-specific rate coefficients of vibrational energy transfer and dissociation. Unlike most of the previous efforts that utilize only the lowest and supposedly most reactive 1A' O PES [A. Varandas and A. Pais, Mol. Phys. 65, 843 (1988)], this paper demonstrates the necessity to account for a complete ensemble of all excited O PESs that correlate with O(X) and O(P) when high-temperature kinetics is of interest. At the same time, it is found that the Varandas 1A' O PES adequately describes vibrational energy transfer and dissociating dynamics when compared to the most recent 1A' O PES by Varga et al. [J. Chem Phys. 147, 154312 (2017)]. The differences between this new dataset and previous rate coefficients are quantified by the master equation model.
通过分子动力学研究了高温下O - O系统中振动弛豫和解离的机制。从第一性原理量子力学计算[瓦尔加等人，《化学物理杂志》147, 154312 (2017)]获得的最新O势能面（PESs），用于推导一套完整的特定状态振动能量转移和解离速率系数。与大多数先前仅使用最低且假定最具反应性的1A' O PES的研究[A. 瓦兰达和A. 派斯，《分子物理学》65, 843 (1988)]不同，本文表明，当关注高温动力学时，有必要考虑与O(X)和O(P)相关的所有激发O PES的完整集合。同时，发现与瓦尔加等人[《化学物理杂志》147, 154312 (2017)]最新的1A' O PES相比，瓦兰达1A' O PES能够充分描述振动能量转移和解离动力学。通过主方程模型对这个新数据集与先前速率系数之间的差异进行了量化。
