Studies of Vibrationally and Rotationally Exited Polyatomic Molecules Using Almost Degenerate Perturbation Theory

这个理论与计算化学项目将研究分子内旋转和振动能量的再分配，这是化学动力学许多方面的关键组成部分。随着激光的出现，这些化学事件现在可以在状态到状态的水平上进行实验审查。本研究的目的是发展理论方法来阐明这种能量流的机制和途径。将发展几乎简并微扰理论的方法，以允许研究迄今为止其他方法无法达到的状态的能量状态和密度。这将允许确定多重共振相互作用与状态密度增加相结合的影响如何导致与反应速率理论相关的统计性质。

This project in the Theoretical and Computational Chemistry Program will investigate intramolecular redistribution of rotational and vibrational energy, a key component in many aspects of chemical dynamics. With the advent of the laser, these chemical events can now be experimentally scrutinized at the state-to-state level. The objective of this research is to develop theoretical methods to elucidate the mechanisms and pathways of this energy flow. The method of Almost Degenerate Perturbation Theory will be developed to allow investigation of energy regimes and densities of states hitherto unattainable by other methods. This will allow for determination of how the effects of multiple resonance interactions combined with increasing densities of states leads to the statistical like properties associated with reaction rate theories.