Theoretical Studies of Proton-Coupled Electron Transfer Reactions

质子耦合电子转移反应的理论研究

• 批准号: 1057875
• 负责人: Sharon Hammes-Schiffer
• 金额: $ 44万
• 依托单位: Pennsylvania State Univ University Park
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-07-01 至 2013-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1057875&HistoricalAwards=false
• 关键词: Theoretical; Studies; Proton; Coupled; Electron

Sharon Hammes-Schiffer of the Pennsylvania State University is supported by an award from the Theory, Models and Computational Methods program in the Chemistry division to carry out research on theoretical studies of proton-coupled electron transfer (PCET) reactions. The PI and her research group are pursuing four related projects: 1) developing both grid and nuclear-electronic orbital(NEO) methods for analyzing the electron-proton nonadiabatic effects to elucidate the mechanisms of PCET reactions. The degree of electronic nonadiabaticity for the proton transfer reaction provides a quantitative diagnostic for differentiating between hydrogen atom transfer (HAT) and PCET, where HAT is electronically adiabatic and PCET is electronically nonadiabatic. 2) developing methods to calculate electron-proton vibronic couplings to enable the prediction of trends in rate constants and kinetic isotope effects for PCET reactions. 3) developing methods for studying the dynamics of photoinduced PCET reactions. The solvent and solute nuclei are propagated on adiabatic electron-proton vibronic surfaces using a surface hopping method to incorporate nonadiabatic transitions among the adiabatic states 4) modeling the ultrafast dynamics of photo-excited PCET in DNA. Proton-coupled electron transfer (PCET) reactions play a critical role in a wide range of chemical and biological processes, including electrochemistry, photosynthesis, respiration, and enzyme reactions. Software resulting from this project is made widely available to the broader community by being included in the public version of the GAMESS computational chemistry software package. The advances from this research are provided to the public through a website devoted to PCET that contains tutorials, code and interactive Java servletes (https://webpcet.chem.psu.edu).

宾夕法尼亚州立大学的莎朗·哈姆斯·西弗（Sharon Hammes-Schiffer）得到了化学部门的理论，模型和计算方法计划的奖项，以对质子偶联电子转移（PCET）反应进行理论研究进行研究。 PI和她的研究小组正在追求四个相关的项目：1）开发网格和核电子轨道（NEO）方法，用于分析电子 - 普罗替型非绝热效应以阐明PCET反应的机制。质子转移反应的电子非绝热程度为区分氢原子转移（HAT）和PCET的定量诊断提供了一种定量诊断，其中HAT具有电子绝热，而PCET是电子非绝热的。 2）开发方法来计算电子蛋白振动耦合，以预测速率常数和动力学同位素效应PCET反应的趋势。 3）开发用于研究光诱导的PCET反应动力学的方法。溶剂和溶质核使用表面跳跃方法在绝热的电子普罗氏蛋白振动表面上传播，以在绝热状态之间掺入非绝热的过渡4）对DNA中光激发PCET的超快动力学进行建模。 质子耦合电子转移（PCET）反应在广泛的化学和生物学过程中起着至关重要的作用，包括电化学，光合作用，呼吸和酶反应。 该项目产生的软件通过包含在游戏计算化学软件包的公共版本中，可以广泛地向更广泛的社区使用。 这项研究的进步通过专门针对PCET的网站提供给公众，该网站包含教程，代码和交互式Java Servletes（https://webpcet.chem.psu.edu）。