...
  • 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Predominance of Nonequilibrium Dynamics in the Photodissociation of Ketene in the Triplet State
【24h】

Predominance of Nonequilibrium Dynamics in the Photodissociation of Ketene in the Triplet State

机译：非平衡动力学在三重态态酮的光解离中的优势

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

The photodissociation of ketene is studied using direct surface-hopping classical trajectories where the energ) and gradient are computed on the fly by means of state-averaged complete active space self-consistent fiel< with a double-~ polarized basis set. Three low-lyingelectron~c states, singlets So and .SI and triplet Tl~ art involved in the process of photodissociation of triplet state ketene. We propagated a trajectory , starting at tht Franck-Condon geometry on SI, and branched it out into many child trajectories every time the propagatin! potential energy surface (PES) crossed with another PES. The major photodissociation pathway to the triple' products was found to be SI -So- TI -CH2(X3BJ + CO(XI~+). It has been found that (1) the So-T nonadiabatic transition creates the Ti species nonstatistically at restricted regions of phase space and (2) ~ large fraction of the T I species thus created dissociates almost immediately, leaving no time forequilibratior of intemal degrees of freedom. Whether a specific Tl trajectory dissociates fast or not is determined by the amount of.C-C stretch vibration at the So-TI branch point. In essence, the above observations suggesl strongly that the TI photodissociation process is highly nonstatistical, thus making equilibrium-based statistica theories inapplicable for computing the dissociation rate.
机译：使用直接表面跳变的经典轨迹研究乙烯酮的光解离，其中通过状态平均的具有双极化基集的完整活性空间自洽场，动态计算能量和梯度。三重态乙烯酮的光解离过程涉及三个低电子态，单重态So和.SI和三重态Tl_art。我们传播了一条轨迹，从SI上的Franck-Condon几何开始，并在每次宣传时将其分支成许多子轨迹！势能面（PES）与另一个PES交叉。发现三元产物的主要光解离途径是SI -So- TI -CH2（X3BJ + CO（XI〜+）。已发现（1）So-T非绝热转变在非统计上产生Ti物种。相空间的受限区域和由此产生的（2）〜很大一部分TI物种几乎立即解离，没有时间使内部自由度达到平衡，特定的T1轨迹是否快速解离取决于CC拉伸量本质上，上述观察结果强烈表明TI光解离过程是高度非统计的，因此基于平衡的统计理论不适用于计算解离速率。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号