Quantum State Resolved Dynamics of Surface Reactions

新墨西哥州大学的Hua Guo获得了化学系化学理论，模型和计算方法项目的奖励，以开发和应用最先进的理论方法来研究气体分子和金属催化剂之间界面处发生的重要基元反应的动力学。 这种反应在现代社会中发挥着越来越重要的作用。用于生产氨的Bosch-Haber工艺、汽车催化转化器、微芯片制造和天然气蒸汽重整制氢是一些众所周知的例子。然而，我们对界面反应的机制和动力学的理解仍然有限。这在很大程度上是因为我们缺乏分子水平上的基本过程的知识。 更好地理解这些基本过程不仅会丰富我们的知识，而且可能有助于设计新的和更有效的催化剂和更好地控制催化反应。 本科生，研究生和博士后同事参与这项研究。 具体而言，该提案旨在彻底了解表面反应的量子态解析动力学，如解离化学吸附和Eley-Rideal反应，使用最先进的理论模型和为这些过程开发的工具。在上一个资助期取得突破的基础上，目前的研究计划侧重于准确确定气相物质与金属表面相互作用的全维Born-Oppenheimer势能面，基于大量的密度泛函理论点，以及这些势能面上的高维量子动力学计算。这些研究代表了一个系统和全面的方法，基本的表面反应动力学，并有望在多原子系统中的能量流，激活机制，以及模式特异性和键选择性的起源有价值的光。在这些研究中获得的见解也可能建议未来的战略，以控制界面化学。此外，这些高层次的理论提供了更近似的动态模型的基准，并有望刺激其他表面反应的理论研究。从这项研究中产生的计算机代码和势能面将提供给更广泛的社区。

Hua Guo of the University of New Mexico is supported by an award from the Chemical Theory, Models and Computational Methods program in the Chemistry Division to develop and apply state-of-the art theoretical approaches to study the dynamics of important elementary reactions occurring at the interface between gas molecules and metal catalysts. Such reactions play an increasingly important role in modern society. The Bosch-Haber process for producing ammonia, automobile catalytic converters, microchip manufacture, and hydrogen generation from steam reforming of natural gas are a few well-known examples. Yet our understanding of the mechanism and dynamics of interfacial reactions remains limited. This is largely because our lack of knowledge of elementary processes at the molecular level. A better understanding of these elementary processes will not only enrich our knowledge, but might also help the design of new and more efficient catalyst and better control of the catalytic reactions. Undergraduate, graduate students and postdoctoral associates participate in this research. Specifically, this proposal aims at a thorough understanding of quantum state resolved dynamics of surface reactions such as dissociative chemisorption and Eley-Rideal reactions, using state-of-the-art theoretical models and tools developed for these processes. Building on breakthroughs achieved in the previous funding period, the current research program focuses on the accurate determination of full-dimensional Born-Oppenheimer potential energy surfaces for the interaction of gas phase species with metal surfaces based on large numbers of density functional theory points, and high-dimensional quantum dynamics calculations on these potential energy surfaces. These studies represent a systematic and comprehensive approach to fundamental surface reaction dynamics and are expected to shed valuable light on the energy flow in the polyatomic system, activation mechanism, and the origin of the mode specificity and bond selectivity. Insights gained in these studies may also suggest future strategies to control interfacial chemistry. In addition, these high-level theories offer benchmarks for more approximate dynamic models and are expected to stimulate theoretical studies of other surface reactions. The computer codes and potential energy surfaces resulting from this research will be available to the broader community.