Collaborative Research: Infra-red Control of Electron Transfer Mechanisms

在这个由化学系化学结构、动力学机制B项目资助的合作项目中，大卫N.杜克大学化学系的Beratan和Peng Zhang以及Igor V. Rubtsov和Russell H.杜兰大学化学系的Schmehl正在开发新的方法来控制电荷在分子中的流动。 分子尺度的电子转移在自然发生的反应和具有技术意义的装置中是必不可少的。 在分子尺度上调节电子运动速率和控制这些反应的方向性的能力是一个重大挑战，可以为太阳能转换、理解生物能量转换方案以及为具有技术意义的设备开发新策略开辟新的策略。 该项目包括化学合成，超快光谱和理论之间的密切合作，为学生建立一个非常丰富的跨学科培训环境。 该团队正在通过为经济弱势群体和历史上代表性不足的群体提供夏季研究机会来促进科学和教育。 此外，新的课程开发涉及多所大学，多个教师的课程教学，解决基础研究的化学和物理原理。该项目的总体目标是了解使用红外微扰在分子尺度上控制电荷流的化学和物理方法。 该研究还包括设计新的分子结构，其中电荷流受到红外辐射的强烈影响。该项目结合了理论和实验方法的力量来操纵分子中的电荷流。研究人员在实验室中使用超快多脉冲光谱方法来驱动和干扰供体-桥-受体化合物的反应动力学。制备和研究了几类给体-桥-受体分子体系，包括过渡金属配合物、双稳态配合物、氢键体系和双稳态桥体系。使用新开发的非平衡分子动力学的方法，在实验室中检查相同的分子系统进行模拟，针对理解振动激发，可能会扰乱反应坐标运动和供体-受体电子耦合相互作用的发展。

In this collaborative project funded by the Chemical Structure, Dynamics & Mechanisms B Program of the Chemistry Division, Professors David N. Beratan and Peng Zhang of the Department of Chemistry at Duke University and Professors Igor V. Rubtsov and Russell H. Schmehl of the Department of Chemistry at Tulane University are developing novel ways to control the flow of electrical charge through molecules. Electron transfer at the molecular scale is essential in naturally occurring reactions and in devices of technological significance. The ability to dial in the rate of electronic motion and to control the directionality of these reactions on the molecular scale is a significant challenge that could open up new strategies for solar energy conversion, for understanding of biological energy conversion schemes, and for developing new strategies for devices of technological significance. The project includes intensive collaborations among chemical synthesis, ultrafast spectroscopy, and theory to establish a very rich interdisciplinary training environment for students. The team is promoting science and education by providing summer research opportunities to economically-disadvantaged and historically underrepresented groups. In addition, novel curriculum developments involve multi-university, multi-faculty teaching of courses that address the chemical and physical principles underpinning the research. The overall aim of the project is to understand the chemical and physical approaches that use infrared perturbations to control charge flow at the molecular scale. The research also includes the design of novel molecular structures where the charge flow is strongly influenced by the infra-red radiation. The project combines the power of theoretical and experimental approaches to manipulate charge flow in molecules. The researchers use ultrafast multi-pulse spectroscopic methods in the laboratory to drive and to perturb the reaction dynamics of donor-bridge-acceptor compounds. Several classes of donor-bridge-acceptor molecular systems are prepared and studied, including transition-metal complexes, bimetallic complexes, hydrogen-bonded systems, and systems with bi-stable bridges. Using newly developed methods of non-equilibrium molecular dynamics, the same molecular systems examined in the experimental laboratory are simulated, targeting the development of understanding vibrational excitation that may perturb both reaction coordinate motion and donor-acceptor electronic coupling interactions.