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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >A cinoarative classical-quantum study of the photodissociation of water in the B band
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A cinoarative classical-quantum study of the photodissociation of water in the B band

机译：B波段水的光解离的经典光学研究

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摘要

A detailed comparison between three-dimensional classical surface hopping calculations and quantum mechanical calculations is presented for the photodissociation of water in the B band.Accurate coupled diabatic potential energy surfaces are used in these calculations.Tully's "fewest seitches"method using an adiabatic representation for the electronic staes is applied for the surface hopping procedure.Studies are the energy dependence of the banching ratios for the possible fragmentation channels,including electronically nonadiabatic channels,and the probabilities for particular vibrational or rotational product staes of the electronically excited OH(A) fragment.Although the classical results generally agree well with the quantum results,some serious errors in the calssical calculations were detected.First,it is found that the calculated fractions for the O(~1D)+H_2 and O(~3P)+H+H fragments are too large.Second,the absence of quantization of the vibrational energy in classical mechanics has consequences for the details of the rotational product state distribution of the OH(A,v=0)fragments.This is important for the "single N phenomenon",and experimentally observed strong preference for populating the highest rotational product state for which the rotational barrier energy is lower than the avilable energy (S.A.Harich,X.F.Yang,R van Harrevelt,and M.C.van Hemert,Phys,Rev.Lett.2001).For a two-dimensional model,where the above-mentioned problems of claddical trajectory calculations do not occur,excellent agreement between classical and quantum results is found.Classical trajectories were followed to explain the single N phenomenon and the origin of the experimentally observed vibrational excitation of OH(A) fragments.
机译：对B带中水的光离解进行了三维经典表面跳变计算与量子力学计算的详细比较。在这些计算中使用了精确耦合的绝热势能表面。研究对象是可能的碎裂通道（包括电子非绝热通道）的结合比率与能量的相关性，以及电子激发的OH（A）碎片的特定振动或旋转产物的概率尽管经典结果与量子结果基本吻合，但在算术计算中发现了一些严重错误。首先，发现O（〜1D）+ H_2和O（〜3P）+ H +的计算分数H片段太大。第二，经典力学中没有振动能量的量化对OH（A，v = 0）片段的旋转产物状态分布的细节有影响。这对于“单N现象”很重要，并且实验观察到强烈倾向于填充旋转的最高旋转产物状态。势垒能量低于势能（SAHarich，XFYang，R van Harrevelt，and MCvan Hemert，Phys，Rev.Lett.2001）。对于二维模型，上述的包层轨迹计算问题遵循经典轨迹来解释单个N现象以及实验观察到的OH（A）碎片的振动激发的起源。

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