Molecular Structure and Dynamics beyond the Born-OppenheimerApproximation

实验物理化学计划支持教授 格兰特在一个持续的实验和理论研究 束缚态表面相交及其对 孤立分子的激发态动力学。 的目的 这项工作是为了更全面地了解 电子运动与核运动耦合的结果 在孤立的分子和复合物中。 分子内势能面的振动结构 交叉点正在分子实验中进行研究 由激光泵浦并由电离探测的光束 里德伯吸收光谱与零动能 光电子能谱学 正在调查的系统包括 各种三原子和多原子;多共振技术 可以分辨出 详细 理论工作正在扩展现有能力 用于处理大的对角化，以允许求解 三态多模问题 技术也正在 开发以获得无辐射的经典类似物 振动混合价态动力学 三原子学 贝瑞的阶段也正在调查中， 扩展参数空间

The Experimental Physical Chemistry Program supports Professor Grant in a continuing experimental and theoretical study of bound-state surface intersections and their effects upon excited-state dynamics in isolated molecules. The purpose of the work is to develop a more complete understanding of the consequences of coupling betwen electronic and nuclear motion in isolated molecules and complexes. The vibrational structure of intramolecular potential surface intersections is being studied experimentally in molecular beams pumped by lasers and probed by ionization-detected Rydberg absorption spectroscopy and zero-kinetic-energy photoelectron spectroscopy. Systems being investigated include various triatomics and polyatomics; multiresonant techniques can give resolution to a vibrational-rotational level of detail. Theoretical work is extending existing capabilities for handling large diagonalizations to allow the solving of three-state multimode problems. Techniques are also being developed to derive classical analogs for radiationless dynamics of vibronically-mixed valence states of excited triatomics. Berry's phase is also being investigated in extended parameter spaces.