Theoretical Study for the Ground Electronic State of the Reaction OH plus SO -> H SO2
Theoretical Study for the Ground Electronic State of the Reaction OH plus SO -> H SO2
复制标题
OH加SO→H SO2反应基态电子态的理论研究
DOI：
10.1021/acs.jpca.9b05776
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发表时间：
2019
影响因子：
2.9
通讯作者：
Li Jun
中科院分区：
文献类型：
--
作者：
Qin Jie;Liu Yang;Lu D;an;Li Jun
OH + SO→H + so2反应在含硫燃料的燃烧和环境中起着重要的作用。它的反应谱类似于OH + CO→H + CO2的反应谱，是形成深层配合物的典型反应。本文建立了OH + SO→H + so2反应的新势能面（PES），该势能面是基于基于CCSD(T)-F12a/AVTZ增广相关一致极化三重zeta基集（CCSD(T)-F12a/AVTZ）的单、双、微扰三重激励的显相关不受限制耦合簇法计算的约39200个数据点。PES对于两个相同氧原子的排列是不变的，这是由作为神经网络输入层的排列不变多项式保证的。在此基础上，采用准经典轨迹方法研究了H与so2在实验平动能为59 kcal mol-1时的碰撞能量传递。预测的高振动能产生so2的轨迹的大积分截面和so2振动能的居群与最近的实验和理论结果一致。详细分析表明，有两种可能的机制，一种是直接机制（不通过HOSO或hso2井），另一种是间接机制（通过一口或两口井）。后者主要产生具有高振动能的so2。
The reaction OH + SO → H + SO2plays an important role in the combustion of sulfur-containing fuels and the environment. Its reaction profile resembles that of OH + CO → H + CO2, which presents a prototypical reaction with the formation of deep complexes. In this work, a new potential energy surface (PES) for the OH + SO → H + SO2reaction is developed based on ca. 39 200 data points calculated at the level of the explicitly correlated unrestricted coupled cluster method with single, double, and perturbative triple excitations with the augmented correlation-consistent polarized triple zeta basis set (CCSD(T)-F12a/AVTZ). The PES is invariant with respect to the permutation of the two identical oxygen atoms, which is guaranteed by the permutation-invariant polynomials as the input layer of the neural network. Using this PES, the quasiclassical trajectory method is employed to study the collision energy transfer between H and SO2at the experimental translational energy of 59 kcal mol–1. The predicted large integral cross sections for trajectories producing SO2with high vibrational energy and populations of the SO2vibrational energy are in good agreement with the recent experimental and theoretical results. Detailed analysis shows that there are two possible mechanisms, a direct mechanism (without passing through HOSO or the HSO2well) and an indirect one (passing through one or both wells). The latter dominates in producing SO2with high vibrational energy.