在中阐明分子内双转移的核量子力学
Yair Litman1, Jeremy O Richardson2, Takashi Kumagai3
1Theory Department , Fritz Haber Institute of the Max Planck Society , Faradayweg 4-6 , 14195 Berlin , Germany.
Journal of the American Chemical Society
|January 17, 2019
概括
量子力学模拟显示在100K以下,协同的双转移 (DHT) 在中占主导地位. 在100-300K之间,协同和阶段性路径竞争,准确地预测反应速率和N-H伸展带.
科学领域:
- 量子化学
- 分子动力学
- 光谱学
背景情况:
- 烯具有复杂的双转移 (DHT) 动态.
- 强烈不和的潜在能量表面需要量子力学处理电子和核.
研究的目的:
- 研究DHT的量子动力学.
- 准确地预测反应速度和振动谱.
- 了解核量子效应的作用.
主要方法:
- 密度函数理论 (DFT) 使用混合函数和范德瓦尔斯校正.
- 量子振动光谱和反应速率的通路整合环聚合物方法.
- 全维环聚合物实时和分子动力学模拟.
主要成果:
- 在100K以下,协同DHT道是主要的.
- 在100-300K之间,由于核量子效应,协调和阶段性路径之间的竞争出现.
- 准确预测基态反应速率 (例如2.19 × 10^11 s^-1在150K).
- 精确地复制N-H延伸带 (约2600厘米^-1).
结论:
- 结合DFT和环聚合物方法的理论方法得到了验证.
- 强的H键,低频模式合和 cis-like 形态影响了 N-H 波段的特性.
- 为理解复杂分子系统中的转移提供了一个框架.
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