Quantum Dynamics of State Preparation, Intramolecular Relaxation, and Unimolecular Reaction of Highly Vibrationally Excited Molecules

理论和计算化学计划中的这个项目涉及高激发态分子的动力学、光谱和光化学的精确量子理论计算。这些研究将对将实验观测数据与详细的分子性质联系起来具有直接的重要性，包括准确描述高能振动模式，根据这些模式指定振动光谱，根据状态特定的单分子反应分析预离解谱，以及用超快脉冲激光制备受激发的分子。高能振动模的研究将用简单的近似方法，如自洽场技术和精确的变分计算。复坐标法的扩展形式将被用来研究振动预解离共振，以确定分子耦合和支配单分子寿命的动力学。利用光学势能技术研究高态密度分子中的分子内振动共振，以表征脉冲激光产生的高能态。这些状态的动力学也将被计算，以揭示状态制备与单分子动力学竞争的光谱结果。

This project in the Theoretical and Computational Chemistry program concerns exact quantum theoretical calculations of the dynamics, spectroscopy and photochemistry of highly excited molecules. These studies will be of direct importance in relating experimental observables to detailed molecular properties, including the accurate description of high energy vibrational modes, the assignment of vibrational spectra in terms of these modes, the analysis of predissociative spectra in terms of state-specific unimolecular reaction, and the preparation of excited molecules with ultrafast pulsed lasers. Vibrational modes of high energy will be studied both by simple approximate methods such as self-consistent field techniques and by exact variational calculations. Extended versions of the complex coordinate method will be used to study vibrational predissociative resonances for determination of the molecular couplings and dynamics whcih govern the unimolecular lifetime. Intramolecular vibrational resonances in molecules with high state densities will be studied by an optical potential technique to characterize the high energy states prepared by pulsed lasers. The dynamics of such states will also be calculated to reveal the spectroscopic consequences of the competition of state preparation with unimolecular dynamics.