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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Ab Initio Molecular Dynamics Study of the Solvated OHCl~--Complex:Implications for the Atmospheric Oxidation of Chloride Anion to Molecular Chlorine
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Ab Initio Molecular Dynamics Study of the Solvated OHCl~--Complex:Implications for the Atmospheric Oxidation of Chloride Anion to Molecular Chlorine

机译：溶剂化的OHCl〜-Complex的从头算分子动力学研究：常压下氯化物阴离子氧化为分子氯的意义

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摘要

We have studied the OHCl~--complex in a six-water cluster and in bulk liquid water by means of Born-Oppenheimer molecular dynamics based on generalized gradient-corrected BLYP density functional theory.Self-interaction-corrected results,which predict a hydrogen-bonded OH…Cl~--complex,are compared to the uncorrected results,which predict a hemibonded(HO-Cl)~-.A second-order Moller-Plesset potential energy landscape of the gas-phase complex in its ground-state was computed to determine which of the two configurations represents the true nature of the complex.Because no evidence of a local minimum was found in the vicinity of the geometry corresponding to(HO-Cl)~-,we conclude that the self-interaction-corrected results are more accurate and,therefore,that the complex is held together by a hydrogen-bond-like interaction in both an asymmetric solvation environment,as represented by the cluster,and a symmetric solvation environment,as represented by the bulk system.We postulate that the mechanism that governs the atmospheric oxidation of Cl~-(aq)to Cl2(g)on the surface of marine aerosols is initiated by the formation of a H-bonded OH…Cl~-complex.Furthermore,because no evidence of charge transfer from Cl~-to OH was found,in either the liquid or the cluster environment,we propose that the second step of the oxidation of Cl~-is the reaction of the complex with a second Cl~-,resulting in the formation of the species Cl_2~-and OH~-.Cl2(g)could then be formed via an electron-transfer reaction with an impinging OH molecule.
机译：我们基于广义梯度校正的BLYP密度泛函理论，通过Born-Oppenheimer分子动力学研究了六水簇和大块液态水中的OHCl〜-络合物。自相互作用校正的结果可预测氢键合的OH…Cl〜-络合物与未校正的结果进行了比较，预测了半键合的（HO-Cl）〜-。气相复合物在基态下的二阶Moller-Plesset势能态通过计算确定这两种构型中的哪一种代表了复合物的真实性质。由于在（HO-Cl）〜-对应的几何附近没有发现局部极小值的证据，我们得出以下结论：校正后的结果更准确，因此，在以簇为代表的非对称溶剂化环境和以本体系统为代表的对称溶剂化环境中，络合物通过氢键状相互作用而结合在一起。假设机器通过形成氢键的OH…Cl〜络合物，引发了控制Cl〜-（aq）在大气中从海洋气溶胶表面氧化为Cl2（g）的无序现象。此外，因为没有证据表明在液态或团簇环境中都发现了Cl〜-OH，我们认为Cl〜-氧化的第二步是配合物与第二Cl〜-的反应，导致物种的形成。然后可以通过与撞击的OH分子的电子转移反应形成Cl_2〜-和OH〜-.Cl2（g）。

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