Barriers, thresholds, and resonances: Spectral quantization of the transition state for the collinear D+H2 reaction
Barriers, thresholds, and resonances: Spectral quantization of the transition state for the collinear D+H2 reaction
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势垒、阈值和共振：共线 D H2 反应过渡态的光谱量化
DOI：
10.1063/1.469391
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发表时间：
1995
影响因子：
4.4
通讯作者：
R. T. Skodje
中科院分区：
文献类型：
--
作者：
R. Sadeghi;R. T. Skodje
在DMBE势能面上，我们分析了共线D+ H_2反应在过渡态区域的量子动力学。利用光谱量子化方法，通过一系列假设的Franck-Condon谱，映射出过渡态的动力学特征。这些光谱是由时间相关的波包动力学产生的。光谱的综合分析揭示了与（1）常规反应性共振，（2）阈值异常和（3）势垒共振相关的三种不同类型的峰。光谱中的各个峰通过使用与时间无关的波函数来分配，所述波函数通过在峰值能量处对波包进行傅里叶变换来获得。的位置，寿命，和波函数提取的所有23个传统的和势垒共振。提出了一个新的解析线形公式来拟合势垒共振谱峰。精确的量子分析也补充了半经典的…
We have analyzed the quantum dynamics of the collinear D+H2 reaction in the region of the transition state on the DMBE potential energy surface. Using the spectral quantization method, the dynamical features of the transition state are mapped out through a sequence of hypothetical Franck–Condon spectra. These spectra are generated by time‐dependent wave packet dynamics. A comprehensive analysis of the spectra has revealed three distinct classes of peaks associated with (1) conventional reactive resonances, (2) threshold anomalies, and (3) barrier resonances. Individual peaks in the spectra are assigned through the use of time‐independent wave functions which are obtained by Fourier transformation of the wave packet at the peak energies. The positions, lifetimes, and wave functions are extracted for all 23 conventional and barrier resonances. A new analytic line shape formula is developed to fit the spectral peaks of the barrier resonances. The exact quantum analysis is also supplemented with a semiclassic...