CAREER: Unraveling Chemical Consequences of Non-adiabatic Energy Transfer at the Gas-Surface Interface

职业：揭示气体-表面界面非绝热能量转移的化学后果

• 批准号: 1753273
• 负责人: Sharani Roy
• 金额: $ 62.45万
• 依托单位: University of Tennessee Knoxville
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-02-01 至 2024-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1753273&HistoricalAwards=false
• 关键词: CAREER; Unraveling; Chemical; Consequences; Non

Sharani Roy of the University of Tennessee is supported by a CAREER award from the Chemical Theory, Models and Computational Methods program in the Chemistry Division to theoretically investigate the role of nonadiabatic energy transfer in chemical processes at the gas-surface interface. Chemistry at solid surfaces and interfaces is the foundation of a wide range of technologies ranging from heterogeneous catalysis, gas storage, and chemical sensing, to nanoelectronics, nanolithography, and solar cells. It also governs natural phenomena, such as corrosion and oxidation processes, e.g., the rusting of iron and the weathering of rocks. Even interstellar formation of molecules occurs on the surfaces of dust particles. In all the above examples, the fundamental interactions that govern the processes are gas-surface interactions. Each complex surface process is comprised of a series of elementary steps, such as the scattering, adsorption, diffusion, desorption, and reactions of gaseous atoms and molecules on solid surfaces. Therefore, a detailed understanding of the gas-surface interface is essential to explain such diverse surface processes. The Roy group investigates fundamental gas-surface interactions underlying different surface and interface phenomena, with focus on phenomena that involve strong coupling between nuclear motion and electronic motion. This coupling can have important and unexpected consequences on the rates and pathways of chemical processes at surfaces. Dr. Roy's research is integrated with a multi-component education plan that includes the development of courses on computational chemistry, surface chemistry, and high-performance computing in the context of scientific computing. In addition, Dr. Roy plans to organize a symposium on chemical reactions and dynamics at surfaces in collaboration with the Oak Ridge National Laboratory.Theoretical and computational research in surface and interface chemistry often involves studies of chemical dynamics in which the motion of atoms and molecules on surfaces is simulated using classical mechanics. This concept of molecular dynamics (MD) simulations has been very successful in describing gas-surface interactions, and has provided valuable qualitative insight into complicated surface processes. Conventional MD relies on the ubiquitous Born-Oppenheimer or adiabatic approximation, which assumes that nuclear motion is uncoupled from electronic motion. However, there are several fundamentally and industrially important gas-surface systems in which this approximation breaks down. Therefore, it is critical to develop accurate and efficient dynamics methods that can be applied to understand interfacial chemical processes where the adiabatic approximation is weak or invalid. Dr. Roy aims to further develop the 'surface hopping' theoretical method of nonadiabatic dynamics in the context of metal surfaces, and apply it to study strongly nonadiabatic gas-surface phenomena where energy is efficiently transferred between electrons and nuclei. These phenomena include (a) the interaction of hydrogen atoms with a gold surface, (b) the interaction of oxygen atoms with a silver surface, and (c) inelastic electron transport in molecular junctions. The overall goal is to develop a method with broader applicability to surface and interface chemistry that will help to attain a more comprehensive understanding of dynamics beyond the Born-Oppenheimer approximation.

田纳西大学的莎拉尼·罗伊获得了化学系化学理论、模型和计算方法计划颁发的职业奖，该计划从理论上研究非绝热能量转移在气体-表面界面化学过程中的作用。固体表面和界面上的化学是从多相催化、气体储存和化学传感到纳米电子学、纳米光刻和太阳能电池等广泛技术的基础。它还管理自然现象，如腐蚀和氧化过程，如铁锈和岩石风化。甚至星际分子的形成也会发生在尘埃颗粒的表面。在所有上述例子中，支配过程的基本相互作用是气体-表面相互作用。每个复杂的表面过程由一系列基本步骤组成，如气体原子和分子在固体表面的散射、吸附、扩散、解吸和反应。因此，对气体-表面界面的详细了解对于解释这种不同的表面过程是至关重要的。罗伊小组研究不同表面和界面现象背后的基本气体-表面相互作用，重点是涉及核运动和电子运动之间强耦合的现象。这种耦合可能会对表面化学过程的速度和路径产生重要的和意想不到的后果。罗伊博士的研究与一个多组成部分的教育计划相结合，该计划包括在科学计算的背景下开发计算化学、表面化学和高性能计算课程。此外，罗伊博士计划与橡树岭国家实验室合作组织一次关于表面化学反应和动力学的研讨会。表面和界面化学的理论和计算研究通常涉及化学动力学的研究，其中原子和分子在表面上的运动是使用经典力学模拟的。分子动力学(MD)模拟的这一概念在描述气体-表面相互作用方面非常成功，并为复杂的表面过程提供了有价值的定性见解。传统的MD依赖于普遍存在的Born-Oppenheimer或绝热近似，该近似假设核运动与电子运动是不耦合的。然而，在几个基本的和工业上重要的气体表面系统中，这种近似被打破。因此，发展准确而有效的动力学方法来理解绝热近似较弱或无效的界面化学过程是至关重要的。罗伊博士的目标是在金属表面的背景下进一步发展非绝热动力学的表面跳跃理论方法，并将其应用于研究强烈的非绝热气体表面现象，即能量在电子和原子核之间有效转移。这些现象包括(A)氢原子与金表面的相互作用，(B)氧原子与银表面的相互作用，以及(C)分子结中的非弹性电子输运。总的目标是开发一种对表面和界面化学具有更广泛适用性的方法，这将有助于更全面地理解超越Born-Oppenheimer近似的动力学。

项目成果

Insight into Subsurface Adsorption Derived from a Lattice-Gas Model and Monte Carlo Simulations

• DOI: 10.1021/acs.jpcc.2c00342
• 发表时间: 2022-03
• 期刊: The Journal of Physical Chemistry C
• 作者: Carson J Mize;Lonnie D. Crosby;Sara B. Isbill;Sharani Roy

Correction: Interfacial acidity on the strontium titanate surface: a scaling paradigm and the role of the hydrogen bond

修正：钛酸锶表面的界面酸度：缩放范式和氢键的作用

• DOI: 10.1039/d1cp90253a
• 发表时间: 2022
• 期刊: Physical Chemistry Chemical Physics
• 影响因子: 3.3
• 作者: Chapleski, Robert C.;Chowdhury, Azhad U.;Mason, Kyle R.;Sacci, Robert L.;Doughty, Benjamin;Roy, Sharani
• 通讯作者: Roy, Sharani