描述HPCO在S1频段中的光解离动态
Jiayuan Li1, Siting Hou1, Changjian Xie1
1Institute of Modern Physics, Shaanxi Key Laboratory for Theoretical Physics Frontiers, Northwest University, Xi'an, Shaanxi 710127, China.
The Journal of chemical physics
|February 19, 2025
概括
本研究为HPCOCO提出了一个新的潜在能量表面 (PES).
科学领域:
- 化学物理 化学物理
- 计算化学的计算化学
- 摄影化学的使用.
背景情况:
- 了解像HPCO这样的分子的兴奋状态动态对于预测它们的反应性至关重要.
- 之前的研究可能缺乏高维的潜在能量表面来准确的动态模拟.
研究的目的:
- 为HPCO的第一个激发状态 (S1(1A′′)) 开发一个全维的潜在能量表面 (PES).
- 通过对新的PES进行准经典轨迹计算,研究HPCO的光解离动力学.
主要方法:
- 使用多参考配置交互 (MRCI) 与戴维森校正和增强相关性一致的极化价值三倍泽塔 (aug-cc-pVTZ) 基础集的初始计算.
- 通过神经网络方法,从超过51000个初始点构建全维的PES.
- 准经典轨迹 (QCT) 计算以模拟光解离动力学.
主要成果:
- PES揭示了能源依赖的产品分布,HP + CO 在低能耗时受到青,H + PCO 在更高能耗时受到青.
- 由于排斥性PES,HP + CO的转换能量分布较高,而H + PCO显示较低的转换能量.
- 对于HP和CO的振动分布均为单调的衰变,旋转分布是冷的,与排斥潜力一致.
结论:
- 开发的PES准确地描述了HPCO的光解离动态.
- 产品分支比率和能量分布对系统的总能量敏感.
- 类似的HP和CO的振动频率,以及CO的较小的旋转常数,影响它们各自的产物状态分布.
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