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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Direct Dynamics Simulation of Dissociation of the [CH3--I--OH](-) Ion-Molecule Complex
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Direct Dynamics Simulation of Dissociation of the [CH3--I--OH](-) Ion-Molecule Complex

机译：[CH3--I--OH]（-）离子-分子配合物解离的直接动力学模拟

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Direct dynamics simulations were used to study dissociation of the [CH3--I--OH](-) complex ion, which was observed in a previous study of the OH- + CH3I gas phase reaction ( J. Phys. Chem. A 2013 , 117 , 7162 ). Restricted B97-1 simulations were performed to study dissociation at 65, 75, and 100 kcal/mol and the [CH3--I--OH](-) ion dissociated exponentially, in accord with RRKM theory. For these energies the major dissociation products are CH3I + OH-, CH2I- + H2O, and CH3OH + I-. Unrestricted B97-1 and restricted and unrestricted CAM-B3LYP simulations were also performed at 100 kcal/mol to compare with the restricted B97-1 results. The {CH3I + OH-}:{CH2I- + H2O}:{CH3OH + I-} product ratio is 0.72:0.15:0.13, 0.81:0.05:0.14, 0.71:0.19:0.10, and 0.83:0.13:0.04 for the restricted B97-1, unrestricted B97-1, restricted CAM-B3LYP, and unrestricted CAM-B3LYP simulations, respectively. Other product channels found are CH2 + I- + H2O, CH2 + I-(H2O), CH4 + IO-, CH3- + IOH, and CH3 + IOH-. The CH3- + IOH singlet products are only given by the restricted B97-1 simulation and the lower energy CH3 + IOH- doublet products are only formed by the unrestricted B97-1 simulation. Also studied were the direct and indirect atomic-level mechanisms for forming CH3I + OH-, CH2I- + H2O, and CH3OH + I-. The majority of CH3I + OH- were formed through a direct mechanism. For both CH2I- + H2O and CH3OH + I-, the direct mechanism is overall more important than the indirect mechanisms, with the roundabout like mechanism the most important indirect mechanism at high excitation energies. Mechanism comparisons between the B97-1 and CAM-B3LYP simulations showed that formation of the CH3OH---I- complex is favored for the B97-1 simulations, whereas formation of the HO----HCH2I complex is favored for the CAM-B3LYP simulations. The unrestricted simulations give a higher percentage of indirect mechanisms than the restricted simulations. The possible role of the self-interaction error in the simulations is also discussed. The work presented here gives a detailed picture of the [CH3--I--OH](-) dissociation dynamics and is very important for unraveling the role of [CH3--I--OH](-) in the dynamics of the OH-(H2O)(n=1,2) + CH3I reactions.
机译：直接动力学模拟用于研究[CH3--I-OH]（-）络合离子的解离，这是在先前对OH- + CH3I气相反应的研究中观察到的（J. Phys。Chem。A 2013 ，117，7162）。根据RRKM理论，进行了受限的B97-1模拟，以研究65、75和100 kcal / mol的解离和[CH3--I-OH]（-）离子呈指数解离。对于这些能量，主要的离解产物是CH3I + OH-，CH2I- + H2O和CH3OH + I-。还以100 kcal / mol进行了无限制的B97-1以及无限制和无限制的CAM-B3LYP模拟，以与受限制的B97-1结果进行比较。 {CH3I + OH-}：{CH2I- + H2O}：{CH3OH + I-}乘积比为0.72：0.15：0.13、0.81：0.05：0.14、0.71：0.19：0.10和0.83：0.13：0.04受限制的B97-1，不受限制的B97-1，受限制的CAM-B3LYP和不受限制的CAM-B3LYP模拟。发现的其他产品渠道为CH2 + I- + H2O，CH2 + I-（H2O），CH4 + I-，CH3- + IOH和CH3 + IOH-。 CH3- + IOH单峰产物仅通过受限的B97-1模拟给出，而较低能的CH3 + IOH-二重峰产物仅通过无限制B97-1模拟给出。还研究了形成CH3I + OH-，CH2I- + H2O和CH3OH + I-的直接和间接原子级机理。大多数CH3I + OH-是通过直接机理形成的。对于CH2I- + H2O和CH3OH + I-而言，直接机理总体上比间接机理更为重要，而在高激发能下，类似like回的机理是最重要的间接机理。 B97-1和CAM-B3LYP模拟之间的机理比较表明，B97-1模拟有利于CH3OH --- I-配合物的形成，而CAM-有利于HO ---- HCH2I配合物的形成。 B3LYP模拟。不受限制的模拟比受限制的模拟提供更高百分比的间接机制。还讨论了自交互误差在仿真中的可能作用。此处介绍的工作详细介绍了[CH3--I-OH]（-）的解离动力学，对于揭示[CH3--I-OH]（-）在动力学中的作用非常重要。 OH-（H2O）（n = 1,2）+ CH3I反应。

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