权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

STUDY OF REACTION DYNAMICS OF O(^1D) ATOM VIA THE COMPLETE ROVIBRATIONAL STATE DISTRIBUTION OF REACTION PRODUCTS

通过反应产物的完整旋转振动态分布研究O(^1D)原子的反应动力学

基本信息

批准号：
13640511
负责人：
FUJIMURA Yo
金额：
$ 2.18万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13640511/
关键词：
Oxygen atom Nitrous oxide Nitric oxide Oxygen molecule Nitrogen molecule Gas-phase elementary reaction Rovibrational distribution Quasi-classical trajectory calculation 反応動力学レーザー分光

项目摘要

To investigate the dynamics of reactions of O(^1D) atom with simple molecules is indispensable to understand gas-phase chemical reactions form the first principle. This study is especially focused on the O(^1D) + N_2O reaction. The reaction of O(^1D) with N_2O has two product channels(i) NO + NO and (ii) N_2 + O_2. The channel (i) have larger branching ratio than channel (ii) and this channlel is the major source of the stratospheric NO.We have fully determined the rotational state distribution of NO(v=0, 1, 2) products of this reaction via laser-induced fluorescence detection after the production of O(^1D) atom with laser photolysis of N_2O. Collision-free observation was ensured under experimental conditions of low pressure and short pump-probe delay time. It is found that the most part of the rotational distribution is close to the statistical prediction although the population in higher rotational levels j = 100 diminishes more significantly than that of the statistical distributio … More n. The observed statistical trend in the rotational distribution is surprising judging from the absence of very stable intermediates which often enable long lifetime inducing efficient energy transfer within the intermediates. Furthermore, the exothermicity of this reaction of 340 kJ/mol is the largest even among the exothermic O(^1D) reactions typically as large as 180 kJ/mol for OH production. The relation between the observed statistical trend and the release of such large exothermicity without deep potential well is an important question in the reaction dynamics. To obtain deeper insight in this issue, we performed quasi-classical trajectory calculation on an ab initio potential surface. It is suggested that the near-statistical energy distribution in the intermediate in the former half of the reaction and exit channel interaction prohibits the high rotational excitation of the product.We have obtained elementary information to detect the N_2 + O_2 channel under jet expansion and multi-photon ionization spectroscopy. Less

研究O（^1D）原子与简单分子反应的动力学是从第一性原理出发理解气相化学反应的必要条件。本研究重点研究了O（^1D）+ N_2O反应。O（^1D）与N_2O的反应有两个产物通道（i）NO + NO和（ii）N_2 + O_2。通道（i）比通道（ii）具有更大的分支比，是平流层NO的主要来源。在激光光解N_2O生成O（^1D）原子后，我们用激光诱导荧光检测方法，全面测定了该反应产物NO（v=0，1，2）的转动态分布。在低气压和短泵浦-探测延迟时间的实验条件下，保证了无碰撞观测。结果表明，尽管在较高的转动水平j = 100时，粒子数的减少比统计分布的减少更为显著，但转动分布的大部分与统计预测接近. ...更多信息 n.在旋转分布中观察到的统计趋势是令人惊讶的，从非常稳定的中间体的存在下，这往往能够长寿命诱导有效的能量转移的中间体的判断。此外，340 kJ/mol的该反应的放热性是最大的，甚至在放热O（^1D）反应中，对于OH的产生通常高达180 kJ/mol。在没有深势阱的情况下，观测到的统计趋势与如此大的介电常数的释放之间的关系是反应动力学中的一个重要问题。为了更深入地理解这个问题，我们在从头算势面上进行了准经典轨道计算。结果表明，前半反应中间体的近统计能量分布和出口通道相互作用抑制了产物的高转动激发，为N_2 + O_2通道的喷流膨胀和多光子电离光谱探测提供了基本信息。少