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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Quasiclassical Trajectory Calculations of Acetaldehyde Dissociation on a Global Potential Energy Surface Indicate Significant Non-transition State Dynamics
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Quasiclassical Trajectory Calculations of Acetaldehyde Dissociation on a Global Potential Energy Surface Indicate Significant Non-transition State Dynamics

机译：整体势能表面上乙醛解离的准经典轨迹计算表明重要的非过渡态动力学

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摘要

A recent experimental study[Houston,P.L.;Kable,S.H.Proc.Natl.Acad.Sci.U.S.A.2006,103,16079]of the photodissociation of acetaldehyde(CH3CHO)has suggested two distinct mechanisms for the production of the molecular products CH4+CO.One corresponds to the traditional transition state mechanism and the other to a transition state-skirting path similar to the roaming channel previously reported in formaldehyde.To investigate this theoretically,a full-dimensional potential energy surface(PES)has been constructed.The PES was fit with permutationally invariant polynomials to 135 000 points calculated using coupled cluster theory with single and double excitations and a perturbative treatment of triple excitations[CCSD(T)]and correlation consistent basis sets of double-and triple-zeta quality.To test the accuracy of the PES additional CCSD(T)and multireference configuration interaction calculations were carried out.Quasiclassical trajectory calculations were run on the PES starting at the acetaldehyde equihbrium geometry and also at the conventional transition state(TS)for the molecular products CH4+CO.The former calculations agree well with the experimental results of Houston and Kable;however,those from the TS do not.The implications for a non-transition state,roaming mechanism in this molecule are discussed.
机译：乙醛（CH3CHO）的光解离的最新实验研究[Houston，PL; Kable，SHProc.Natl.Acad.Sci.USA2006,103,16079]提出了两种不同的机制来生产分子产物CH4 + CO一个对应于传统的过渡态机制，另一个对应于类似于先前在甲醛中报道的漫游通道的过渡态过渡路径。从理论上对此进行了研究，构建了一个全尺寸的势能面（PES）。运用置换不变多项式拟合至13.5万点，该多项式是使用具有单激励和双激励的耦合聚类理论以及三激励[CCSD（T）]的扰动处理以及双和三Zeta质量的相关一致基础集计算的。进行了PES附加CCSD（T）的精确度计算和多参考构型相互作用计算。从乙缩醛开始在PES上进行准经典轨迹计算分子结构CH4 + CO的脱水平衡几何形状以及常规过渡态（TS）。以前的计算结果与Houston和Kable的实验结果非常吻合;但是，TS的结果与之不符。讨论了该分子的过渡态，漫游机理。

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