Molecular Networks: Bonding and Long-Range Interactions in Anionic Environments

在化学系化学结构、动力学和机理(CSDM-A)计划的支持下，亚利桑那大学的Andrei Sanov教授和他的团队将研究电子与分子的结合以及由于向扩展的分子网络添加多余电子而引起的协同作用。这种相互作用在环境和生物化学中无处不在，并在塑造我们的世界方面发挥着决定性的作用。通过捕捉激光产生的电子图像，该项目旨在获得对化学本质的统一的分子/超分子观点：电子在稳定分子和经历化学变化的系统中的行为。萨诺夫教授将在这项研究的启发下开展教育活动，将重点放在入门和高级课程级别的科学素养和数学密集型教育上。这些活动将包括将研究元素整合到普通化学、数学物理和物理化学课程中的动手研究暴露和建模项目。这个在亚利桑那大学萨诺夫实验室的项目将专注于团簇阴离子中的化学相互作用，重点是电荷离域以及共价力和非共价力之间的相互作用。由于描述复杂系统必须从了解其构建块开始，因此将使用双管齐下的方法。首先，我们将研究分子内的共价键，包括与周围环境相互作用对分子内键结构的影响。其次，将针对远程共价力和非共价力控制的分子网络中的协同效应。这两个分支之间的协同很重要，因为第一个针对的是化学物质的积木，而第二个分支考虑的是它们如何在更大的结构中结合在一起，超越了分子的观点。该项目将利用光电子成像光谱学与理论建模相结合。光电子能谱和角分布将被用来表征团簇阴离子中的化学键和分子间作用力。这项工作将从非平衡暂态物种中的稳定键发展到自由基和双自由基相互作用，以及团簇和较大分子网络中的弱共价相互作用和溶剂化力。结果将借助电子结构计算进行解释。更广泛的影响包括增加对活性中间体的结构和热化学的知识以及更好地了解化学键、电荷共享和反应的一般机制所带来的潜在社会效益。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With support from the Chemical Structure, Dynamics and Mechanisms-A (CSDM-A) program of the Chemistry Division, Professor Andrei Sanov and his team at the University of Arizona will study the binding of electrons to molecules and the cooperative interactions induced by the addition of excess electrons to extended molecular networks. Such interactions are ubiquitous in environmental and biological chemistry and play defining roles in shaping our world. By capturing laser-generated images of the electrons, the project aims to attain a unified molecular/supramolecular view of the essence of chemistry: the behavior of electrons in stable molecules and in systems undergoing chemical change. Professor Sanov will develop educational activities inspired by this research, placing emphasis on science literacy and math-intensive education at the introductory and advanced curriculum levels. These activities will include hands-on research exposure and modeling projects that integrate research elements into the general chemistry, mathematical physics, and physical chemistry coursework.This project in the Sanov laboratory at the University of Arizona will focus on chemical interactions in cluster anions, with an emphasis on charge delocalization and the interplay between covalent and noncovalent forces. Since describing a complex system must start with understanding its building blocks, a two-pronged approach is to be used. First, the intramolecular covalent bonding will be examined, including the effects of interactions with the surroundings on the intramolecular bonding structures. Second, the cooperative effects in molecular networks controlled by long-range covalent and noncovalent forces will be targeted. The synergy between the two prongs is important, for the first is aimed at the building blocks of chemical matter, while the second considers how they fit together in larger structures, transcending the molecular view. The project will utilize photoelectron imaging spectroscopy in conjunction with theoretical modeling. The photoelectron spectra and angular distributions will be used to characterize the chemical bonding and inter-molecular forces in cluster anions. The work will advance from stable bonds to radical and diradical interactions in non-equilibrium transient species, and to weak covalent interactions and solvation forces in clusters and larger molecular networks. The results will be interpreted with the help of electronic-structure calculations. The broader impacts include potential societal benefits from increased knowledge of the structures and thermochemistry of reactive intermediates and an improved understanding of the general mechanisms of chemical bonding, charge-sharing, and reactivity.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.