CAREER: Direct Interrogation of Proton-Coupled Electron Transfer Reaction Dynamics and Mechanisms with Cryogenic Ion and Ultrafast Vibrational Spectroscopies

职业：用低温离子和超快振动光谱直接探究质子耦合电子转移反应动力学和机制

• 批准号: 2044927
• 负责人: Joseph Fournier
• 金额: $ 64.54万
• 依托单位: Washington University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2021
• 资助国家: 美国
• 起止时间: 2021-06-01 至 2026-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2044927&HistoricalAwards=false
• 关键词: CAREER; Direct; Interrogation; Proton; Coupled

With support from the Chemical Structure, Dynamics, and Mechanisms-A (CSDM-A) Program in the Division of Chemistry, Dr. Joseph Fournier and his group at Washington University in St. Louis are using sophisticated laser techniques to study very fast chemical reactions. Specifically, Dr. Fournier’s group is investigating a special class of reactions in which protons and electrons simultaneously move from one molecule to another. These reactions are at the heart of many fundamental biological and chemical processes, including photosynthesis and cellular respiration, but are difficult to study with existing experimental methods. In order to overcome such difficulties, Dr. Fournier and his students are developing a new approach that allows them to directly track the reactions in real time with molecular-level detail. The results of their measurements help to unravel and quantify the most important factors that drive these reactions, which is vital information for understanding key biological processes and for developing new molecules for applications in green energy and chemical synthesis. The project also includes an effort to modernize physical chemistry education at the undergraduate and graduate levels, as well as outreach events that introduce St. Louis-area high school students to the ways in which the quantum mechanical behavior of atoms and molecules affects the world around us. Catalytic processes driven by proton-coupled electron transfer (PCET) reactions are ubiquitous in chemistry and biology, yet the current understanding of these reactions and the ability to quantitatively predict mechanisms and reaction dynamics involving PCET remains limited. Dr. Fournier and his team are using a suite of infrared spectroscopy techniques to study PCET reactions for a series of biomimetic model complexes. These spectroscopic techniques include gas-phase cryogenic ion vibrational spectroscopy (CIVS), solution-phase two-dimensional infrared spectroscopy (2DIR), as well as the development and implementation of a novel approach called time-resolved cryogenic ion vibrational spectroscopy (TR-CIVS). The TR-CIVS measurements will systematically probe well-defined systems in the gas phase with both high frequency resolution and ultrafast temporal resolution, with the goal of characterizing the elusive proton transfer coordinate in more detail than previously possible. The experiments target the identification of transient intermediates and the dynamics of their formation, and will probe the role of tunneling and low-frequency hydrogen-bonding modes in the proton transfer process. This work aims to provide important insight for understanding PCET mechanisms and to aid in the development of new computational models that predict how the chemical architecture of catalytic systems determines their reactive properties.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学系化学结构、动力学和机理 A (CSDM-A) 项目的支持下，圣路易斯华盛顿大学的 Joseph Fournier 博士和他的团队正在使用先进的激光技术来研究非常快的化学反应具体来说，福尼尔博士的小组正在研究一类特殊的反应，其中质​​子和电子同时从一个分子移动到另一个分子，这些反应是许多基本生物和化学过程的核心，包括光合作用和细胞。但用现有的实验方法很难研究这些困难，Fournier 博士和他的学生正在开发一种新方法，使他们能够直接实时跟踪分子水平细节的反应结果。他们的测量有助于揭示和量化驱动这些反应的最重要因素，这是理解关键生物过程和开发用于绿色能源和化学合成的新分子的重要信息。该项目还包括实现物理化学教育现代化的努力。本科生和研究生级别以及外展活动向圣路易斯地区的高中生介绍原子和分子的量子力学行为如何影响我们周围的世界，由质子耦合电子转移（PCET）反应驱动的催化过程在化学和生物学中无处不在。目前对这些反应的理解以及定量预测涉及 PCET 的机制和反应动力学的能力仍然有限。 Fournier 博士和他的团队正在使用一套红外光谱技术来研究一系列仿生的 PCET 反应。这些光谱技术包括气相低温离子振动光谱（CIVS）、溶液相二维红外光谱（2DIR），以及一种称为时间分辨低温离子振动光谱的新方法的开发和实施。 TR-CIVS）。TR-CIVS 测量将以高频分辨率和超快时间分辨率系统地探测气相中明确的系统，目的是表征难以捉摸的质子。该实验的目标是识别瞬态中间体及其形成动力学，并将探讨隧道效应和低频氢键模式在质子转移过程中的作用。对于理解 PCET 机制并帮助开发新的计算模型来预测催化系统的化学结构如何决定其反应性质具有重要的见解。该奖项是 NSF 的法定使命，并通过使用基金会的智力优势和评估进行评估，被认为值得支持。更广泛的影响审查标准。

项目成果

Ultrafast transient vibrational action spectroscopy of cryogenically cooled ions

低温冷却离子的超快瞬态振动作用光谱

• DOI: 10.1063/5.0155490
• 发表时间: 2023-07
• 期刊: The Journal of Chemical Physics
• 作者: Chen, Liangyi;Ma, Zifan;Fournier, Joseph A.
• 通讯作者: Fournier, Joseph A.

Vibrational Dynamics of the Intramolecular H-Bond in Acetylacetone Investigated with Transient and 2D IR Spectroscopy

用瞬态和二维红外光谱研究乙酰丙酮中分子内氢键的振动动力学

• DOI: 10.1021/acs.jpcb.2c00793
• 发表时间: 2022-05
• 期刊: The Journal of Physical Chemistry B
• 作者: Dean, Jessika L.;Fournier, Joseph A.
• 通讯作者: Fournier, Joseph A.

Investigating Intramolecular H Atom Transfer Dynamics in β-Diketones with Ultrafast Infrared Spectroscopies and Theoretical Modeling

用超快红外光谱和理论模型研究β-二酮中的分子内氢原子转移动力学

• DOI: 10.1021/acs.jpca.3c05417
• 发表时间: 2023-11
• 期刊: The Journal of Physical Chemistry A
• 作者: Dean, Jessika L.S.;Winkler, Valerie S.;Boyer, Mark A.;Sibert, Edwin L.;Fournier, Joseph A.
• 通讯作者: Fournier, Joseph A.

Unraveling the Vibrational Spectral Signatures of a Dislocated H Atom in Model Proton-Coupled Electron Transfer Dyad Systems

揭示质子耦合电子转移二元系统模型中位错氢原子的振动光谱特征

• DOI: 10.1021/acs.jpca.3c00524
• 发表时间: 2023-04
• 期刊: The Journal of Physical Chemistry A
• 作者: Chen, Liangyi;Sibert, Edwin L.;Fournier, Joseph A.
• 通讯作者: Fournier, Joseph A.

Origins of the diffuse shared proton vibrational signatures in proton-coupled electron transfer model dyad complexes

质子耦合电子转移模型二元复合物中弥散共享质子振动特征的起源

• DOI: 10.1063/5.0122777
• 发表时间: 2022-10
• 期刊: The Journal of Chemical Physics
• 作者: Chen, Liangyi;Ma, Zifan;Fournier, Joseph A.
• 通讯作者: Fournier, Joseph A.