Tyng Vivian, Kellman Michael E
Department of Chemistry, University of Oregon, Eugene, Oregon 97403, USA.
J Phys Chem B. 2006 Sep 28;110(38):18859-71. doi: 10.1021/jp057357f.
Semiclassical techniques are used to analyze highly excited pure bending vibrational dynamics from spectra of C2H2. An analytic bifurcation approach is developed, based on critical points of a classical version of the quantum fitting Hamiltonian. At high energy four new types of anharmonic modes are born in bifurcations of the normal modes: local, orthogonal, precessional, and counter-rotator. Visual insight into their nature is obtained with the help of computer-generated three-dimensional animations. The connection between the local mode and the acetylene-vinylidene isomerization "reaction mode" is considered.
采用半经典技术从乙炔光谱分析高激发纯弯曲振动动力学。基于量子拟合哈密顿量的经典版本的临界点，开发了一种解析分岔方法。在高能量下，四种新型非谐模式在简正模式的分岔中产生：局域模式、正交模式、进动模式和反向旋转模式。借助计算机生成的三维动画直观地了解它们的性质。考虑了局域模式与乙炔-亚乙烯基异构化“反应模式”之间的联系。
