Analytic perturbative classification and assignment of eigenstates of algebraic vibrational Hamiltonians

被引:7
作者
Diaz, A. [2 ]
Jung, C. [1 ]
机构
[1] Univ Nacl Autonoma Mexico, Inst Ciencias Fis, Cuernavaca 62191, Morelos, Mexico
[2] Univ Nacl Autonoma Mexico, Inst Matemat, Unidad Cuernavaca, Cuernavaca 62191, Morelos, Mexico
关键词
molecular vibrations; canonical perturbation theory; assignment;
D O I
10.1080/00268970801961021
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We show how a classification and assignment for highly excited molecular vibrational states obtained previously by wave function inspection can also be obtained by analytic perturbative methods. This gives additional insight into the meaning of the classification. In addition it allows one to predict beforehand in which region of the spectrum which class of states is to be expected. As examples we present the class of states in DCO which are based on the coupling of the bend with the DC stretch, the class of states of DCO without any coupling and the bend vibrational states of acetylene at both ends of the spectrum within a given polyad. Thereby we learn the exact definition and meaning of the transverse quantum numbers. As a byproduct we get for the nonintegrable original Hamiltonian, integrable approximations which are valid in a restricted region of the phase space classically or for one class of states quantum mechanically.
引用
收藏
页码:787 / 799
页数:13
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