International Collaboration in Chemistry: Non-statisticality, selectivity and phase space structure in organic reactions

康奈尔大学的Gregory Ezra教授得到化学学部化学理论、模型和计算方法项目的支持，与Stephen Wiggins教授（英国布里斯托尔大学）和Barry Carpenter教授（英国卡迪夫大学）进行合作研究。这是国际化学合作奖（ICC），威金斯和卡彭特的研究得到了英国EPSRC的支持。研究人员正在对有机反应中的非统计动力学及其与多原子分子经典哈密顿模型相空间结构的关系进行理论和计算探索。这项工作的动机是最近的实验，利用最先进的方法和哈密顿动力学理论的概念来解决有机反应中的反应性和选择性问题。总体目标是发展相空间方法来理解和最终预测有机分子热反应中的非统计动力学。本研究运用应用动力系统理论的最新理论和计算进展，研究多模分子的反应动力学和相空间结构，探索非统计行为的动力学根源。了解控制选择性的因素对化学合成至关重要，这项工作为正在进行的有机反应机制解释范式转变提供了严格的动力学基础。合作机构之间每年交换博士后，确保参与项目的同事在广泛的研究方法方面接受广泛的跨学科教育，涵盖化学动力学，动力系统和有机反应机制研究的子领域。

Professor Gregory Ezra of Cornell University is supported by the Chemical Theory, Models and Computational Methods program in the Chemistry Division to engage in collaborative research with Prof. Stephen Wiggins (Bristol University, UK) and Professor Barry Carpenter (Cardiff University, UK). This is an International Collaborations in Chemistry (ICC) award, and the research of Wiggins and Carpenter is supported by the UK EPSRC. The researchers are undertaking a theoretical and computational exploration of nonstatistical dynamics in organic reactions and its relation to phase space structure in classical Hamiltonian models for polyatomic molecules. This work, motivated by recent experiments, addresses problems of reactivity and selectivity in organic reactions exploiting state-of-the-art methodology and concepts from the theory of Hamiltonian dynamics. The overall aim is the development of a phase space approach to understanding and ultimately predicting nonstatistical dynamics in thermal reactions of organic molecules. The research applies recent theoretical and computational advances in applied dynamical systems theory to study reaction dynamics and phase space structure in multimode molecules, and to probe the dynamical origins of nonstatistical behavior.Understanding the factors that control selectivity is of essential importance for chemical synthesis, and this work provides a rigorous dynamical foundation for the ongoing paradigm shift in the interpretation of organic reaction mechanisms. Annual exchange of postdocs between collaborating institutions ensures that the coworkers involved in the project receive a broad interdisciplinary education in a wide range of research methodologies, spanning the subfields of chemical dynamics, dynamical systems and the study of organic reaction mechanisms.