Molecular Structure and Dynamics beyond the Born-OppenheimerApproximation

实验物理化学计划支持格兰特教授继续进行束缚态表面交叉点及其对孤立分子激发态动力学的影响的实验和理论研究。这项工作的目的是更全面地理解孤立分子和络合物中电子运动和核运动之间耦合的后果。在激光泵浦的分子束中实验研究了分子内势面交叉的振动结构，并用电离探测里德堡吸收光谱和零动能光电子能谱进行了探测。正在研究的系统包括各种三原子和多原子；多共振技术可以给出细节的振动-旋转水平的分辨率。理论工作是扩展现有的处理大型对角化的能力，以允许解决三态多模问题。还在开发技术来推导经典的类似物，用于激发三原子的振动混合价态的无辐射动力学。Berry的相位也在扩展的参数空间中被研究。

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.