EAPSI: Comparison of Two Different Geometric Techniques for Computing Chemical Reaction Rates

EAPSI：计算化学反应速率的两种不同几何技术的比较

• 批准号: 1614377
• 负责人: Sulimon Sattari
• 金额: $ 0.54万
• 依托单位: Sattari Sulimon
• 依托单位国家: 美国
• 项目类别: Fellowship Award
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-06-15 至 2017-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1614377&HistoricalAwards=false
• 关键词: EAPSI; Comparison; Two; Different; Geometric

Computing chemical reaction rates is a difficult task, especially in complex chemical systems such as combustion. Geometric techniques are promising techniques which use a lower-dimensional slice of the system to estimate the chemical reaction rate. For this project, the researcher will compare two geometric techniques for computing chemical reaction rates called lobe dynamics and transition state theory. The PI will collaborate with Hokkaido University professor Tamiki Komatsuzaki, who is a noted expert on using transition state theory to compute chemical reaction rates. In comparing the two techniques, the PI hopes to help narrow down when each technique should be used to obtain accurate chemical reaction rates. The ionization of hydrogen in external fields resembles a chemical reaction. The atom is injected with some energy, and, if it overcomes a certain threshold, it becomes ionized. The ionization rate can be computed by integrating a representative set of trajectories. For reaction systems with multiple reactants and products, chaos makes it difficult to adequately sample the phase space and accurately compute the reaction rate. Transition state theory and homotopic lobe dynamics are both promising methods for computing reaction rates in chaotic systems, but both methods have their benefits and limitations. Transition state theory computes the reaction rate using a flux across a lower-dimensional surface, requiring fewer trajectories. It assumes, however, that a non-recrossing transition state exists in the system, which does not hold in general. Homotopic lobe dynamics uses the topology of phase space structures to characterize and compute periodic orbits, and then periodic orbit theory is used to compute the reaction rate as a sum over their contributions. The goals of this research are to compare the ranges of validity and computational feasibility of the two methods, and to compute the ionization reaction rate of the hydrogen atom in parallel fields over a wide range of field strengths.This award under the East Asia and Pacific Summer Institutes program supports summer research by a U.S. graduate student and is jointly funded by NSF and the Japan Society for the Promotion of Science.

计算化学反应速率是一项困难的任务，特别是在复杂的化学系统，如燃烧。几何技术是一种很有前途的技术，它使用系统的低维切片来估计化学反应速率。在这个项目中，研究人员将比较两种用于计算化学反应速率的几何技术，称为叶动力学和过渡态理论。PI将与北海道大学教授Tamiki Komatsuzaki合作，Tamiki Komatsuzaki是使用过渡态理论计算化学反应速率的着名专家。在比较这两种技术时，PI希望有助于缩小每种技术的使用范围，以获得准确的化学反应速率。氢在外场中的电离类似于化学反应。原子被注入一定的能量，如果它超过一定的阈值，它就会被电离。电离率可以通过积分一组有代表性的轨迹来计算。对于具有多个反应物和产物的反应系统，混沌使得难以对相空间进行充分采样并精确计算反应速率。过渡态理论和同伦叶动力学都是计算混沌系统反应速率的有前途的方法，但这两种方法都有各自的优点和局限性。过渡态理论使用穿过低维表面的通量来计算反应速率，需要较少的轨迹。然而，它假设在系统中存在一个非再交叉的过渡态，这在一般情况下并不成立。同伦叶动力学使用相空间结构的拓扑来表征和计算周期轨道，然后使用周期轨道理论来计算反应速率作为它们的贡献之和。本研究的目的是比较两种方法的有效性范围和计算可行性，并计算氢原子在平行场中的电离反应率。本研究是由NSF和日本科学促进会共同资助的东亚和太平洋夏季研究所（East Asia and Pacific Summer Institutes）项目，资助美国研究生的夏季研究。