Understanding Vibrational Energy Transfer and Spectra in Microporous and Mesoporous Materials

H区堪萨斯大学的Thompson得到了理论和计算化学项目的支持，部分得到了刺激竞争性研究的实验项目的支持，对微孔和中孔硅酸盐溶胶-凝胶中的振动能量转移和光谱进行了理论研究。 在这项工作中，专注于溶胶-凝胶孔，能量传递过程和振动光谱进行了模拟，正在开发的方法，用于调查的分子水平的机制，并正在探索的孔径，表面化学，溶剂和溶质性质的影响。 在这项研究中，混合量子经典分子动力学模拟，标准微扰理论的方法，和经典的非平衡态分子动力学模拟被用来模拟振动能量转移和光谱的纯液体在溶胶-凝胶孔和双原子和三原子溶质在溶剂中局限于溶胶-凝胶孔。此外，正在开发用于研究振动能量转移和光谱的机制以及有效地估计能量转移速率常数的方法。这项工作将提高纳米结构多孔溶胶-凝胶中的能量转移和红外和拉曼测量的理解，同时准确计算振动光谱和能量转移速率常数，可以与实验结果进行比较。 它还将产生详细的机理信息，这将显着提高能量转移途径的理解，并有助于解释微孔和中孔材料的振动光谱。 在更广泛的影响方面，拟议工作的结果将有助于通过提高对能量流和光谱探针途径的理解来设计和表征微孔和中孔材料。这些都是重要的问题，在一个广泛的，不断增长的，各种各样的纳米结构系统。因此，这项研究将是相关的光谱学，能量传递，热流，和反应性的材料，如微孔和介孔催化剂，超分子组件，模板材料，反胶束，生物系统，水凝胶，膜，燃料电池电极和非线性光学材料。这项工作也应该提供深入了解分子电子，光学和机械设备的能量耗散。

Ward H. Thompson of the University of Kansas is supported by the Theoretical and Computational Chemistry program and partially supported by the Experimental Program To Stimulate Competitive Research to conduct a theoretical investigation of vibrational energy transfer and spectra in microporous and mesoporous silicate sol-gels. In this work focusing on sol-gel pores, energy transfer processes and vibrational spectra are being simulated, methods for investigating the molecular-level mechanisms are being developed, and the effect of pore size, surface chemistry, and solvent and solute properties are being explored. In this study mixed quantum-classical molecular dynamics simulations, standard perturbation theory approaches, and classical nonequilibrium molecular dynamics simulations are being used to simulate vibrational energy transfer and spectra of neat liquids in sol-gel pores and diatomic and triatomic solutes in solvents confined in sol-gel pores. In addition, approaches for investigating the mechanisms of vibrational energy transfer and spectra and efficiently estimating energy transfer rate constants are being developed. This work will improve the understanding of energy transfer and infrared and Raman measurements in nanostructured porous sol-gels while at the same time accurately computing vibrational spectra and energy transfer rate constants that can be compared with experimental results. It will also yield detailed mechanistic information that will significantly improve the understanding of energy transfer pathways and assist in the interpretation of vibrational spectra in microporous and mesoporous materials. In terms of broader impacts, the results of the proposed work will assist in the design and characterization of microporous and mesoporous materials by improving the understanding of both pathways for energy flow and spectroscopic probes. These are important issues in a wide, and growing, variety of nanostructured systems. Thus, this study will be relevant to spectroscopy, energy transfer, heat flow, and reactivity in materials such as microporous and mesoporous catalysts, supramolecular assemblies, templated materials, reverse micelles, biological systems, hydrogels, membranes, fuel cell electrodes, and nonlinear optical materials. This work should also provide insight into energy dissipation in molecular electronic, optical, and mechanical devices.