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

该项目属于理论与计算化学项目，涉及高激发态分子的动力学、光谱学和光化学的精确量子理论计算。这些研究对于将实验观察结果与分子的详细性质联系起来具有直接的重要性，包括高能振动模式的准确描述，根据这些模式分配振动光谱，根据特定状态的单分子反应分析预解离光谱，以及用超快脉冲激光器制备激发态分子。高能量的振动模式将通过简单的近似方法，如自洽场技术和精确的变分计算来研究。复坐标法的扩展版本将用于研究振动预解离共振，以确定控制单分子寿命的分子耦合和动力学。用光势技术研究高态密度分子的分子内振动共振，以表征脉冲激光制备的高能态。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后果。

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.