Theoretical Descriptions of Molecular Dynamics and Spectroscopy in Condensed and Gas Phases

麦迪逊的威斯康星州大学的Edwin Sibert得到了理论和计算化学项目的支持，使用经典和量子技术相结合的方法研究气相和液相中多原子分子的能量流。 这项研究将包括动力学事件，包括振动弛豫，质子转移反应，和振动预解离在凝聚相。 我们的目标是开发这些过程的强大的分子模型。 模型的结果应该是一致的实验观察，并有望作为未来的实验指导。将研究溴仿和氘代溴仿的混合物，目的是绘制出分子之间能量的传播方式。 此外，甲酸二聚体，双质子转移的一个典型例子，将在气相和液相中进行研究。 最后，在凝聚相中的振动预解离，特别是氢键低聚物的预解离，将investigated.Recent进展，在一个超快激光光谱使化学家能够探测到前所未有的时间和尺寸分辨率的分子事件的展开。 当这些实验与从原子论的角度进行的深思熟虑的理论建模相结合时，就能获得关于原子之间的力如何控制能量流的重要见解。这项研究将朝着量化这些想法和开发预测模型的方向取得进展，这些模型是由于这些力量而发生的事件。 这样的模型是必不可少的，从长远来看，在分子水平上的大气，燃烧和生物过程的成功建模。

Edwin Sibert of the University of Wisconsin, Madison, is supported by the Theoretical and Computational Chemistry Program to study energy flow in polyatomic molecules in both gas and liquid phases using combined classical and quantum techniques. The research will encompass dynamical events that include vibrational relaxation, proton transfer reactions, and vibrational predissociation in the condensed phase. The objective is to develop robust molecular models of these processes. The model results should be consistent with experimental observations, and are expected to serve as a guide for future experimentation. Mixtures of bromoform and deuterated bromoform will be investigated with the goal of mapping out how energy travels between molecules. As well, formic acid dimer, a prototypical example of double proton transfer, will be studied in the gas and liquid phases. Finally, vibrational predissociation in the condensed phase, and in particular predissociation of hydrogen bonded oligomers, will be investigated.Recent advances in an ultrafast laser spectroscopies enable chemists to probe the unfolding of molecular events with unprecedented time and size resolution. When these experiments are combined with thoughtful theoretical modeling from an atomistic perspective, significant insights are attained on how energy flow is controlled by forces between atoms. This research will make progress toward quantifying these ideas and developing predictive models for the events that occur as a result of these forces. Such models are essential, in the long term, for successful modeling of atmospheric, combustion, and biological processes at a molecular level.