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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Adiabatic and nonadiabatic bond cleavages in Norrish type i reaction
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Adiabatic and nonadiabatic bond cleavages in Norrish type i reaction

机译：诺里斯I型反应中的绝热和非绝热键裂解

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摘要

One of the fundamental photoreactions for ketones is Norrish type I reaction, which has been extensively studied both experimentally and theoretically. Its α bond-cleavage mechanisms are usually explained in an adiabatic picture based on the involved excited-state potential energy surfaces, but scarcely investigated in terms of a nonadiabatic picture. In this work, the S_1 α bond-cleavage reactions of CH_3OC(O)Cl have been investigated by using the CASSCF and MRCI-SD calculations, and the ab initio based time-dependent quantum wavepacket simulation. The numerical results indicate that the photoinduced dissociation dynamics of CH_3OC(O)Cl could exhibit strong nonadiabatic bond-fission characteristics for the S _1 α C-Cl bond cleavage, while the dynamics of the S_1 α C-O bond cleavage is mainly of adiabatic characteristics. This nonadiabatic mechanism for Norrish type I reaction of CH_3OC(O)Cl is uncovered for the first time. The quantum wavepacket dynamics, based on the reduced-dimensional coupled potential energy surfaces, to some extent illustrates the significance of the nonadiabatic effect in the transition-state region on the dynamics of Norrish type I reaction.
机译：酮的基本光反应之一是Norrish I型反应，已在实验和理论上进行了广泛研究。通常在绝热图中基于所涉及的激发态势能面解释其α键断裂机理，但很少在非绝热图中进行研究。在这项工作中，通过使用CASSCF和MRCI-SD计算以及基于从头算的时变量子波包模拟，研究了CH_3OC（O）Cl的S_1α键断裂反应。数值结果表明，CH_3OC（O）Cl的光致离解动力学表现出较强的S _1αC-Cl键断裂非绝热键裂变特征，而S_1αC-O键断裂的动力学主要是绝热特征。 CH_3OC（O）Cl的Norrish I型反应的这种非绝热机理是首次发现。基于降维耦合势能面的量子波包动力学在一定程度上说明了过渡态区域中非绝热效应对Norrish I型反应动力学的重要性。

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