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

这个理论与计算化学的项目 程序涉及精确的量子理论计算的 动力学、光谱学和光化学 分子。 这些研究将直接对 将实验观测值与详细的分子 属性，包括高能量的准确描述 振动模式，振动光谱的归属， 这些模式的条件下，预离解光谱的分析 在状态特异性单分子反应方面， 用超快脉冲激光制备激发分子。 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。 加长版的 用复坐标方法研究了振动 用于测定分子的预解离共振 控制单分子寿命的耦合和动力学。 高分子中的分子内振动共振 态密度将由光学势来研究 技术来表征高能量状态， 脉冲激光 这些国家的动态也将是 计算揭示了光谱的后果， 状态准备与单分子动力学的竞争。

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.