Christiansen Ove
Department of Chemistry, University of Arhus, DK-8000 Arhus C, Denmark.
J Chem Phys. 2005 May 15;122(19):194105. doi: 10.1063/1.1899156.
A formalism for deriving and implementing response functions for vibrational wave functions is described. The formalism utilizes a recently developed second-quantization formulation of many-mode dynamics to define nonredundant parameterizations for different types of approximate vibrational wave functions. The derived response functions cover the cases of an exact state, a vibrational self-consistent field state, and a vibrational configuration interaction state. Sample calculations are presented for the linear-response function and response excitation energies for a two-mode model system and for formaldehyde employing a quartic force field. The advantages and disadvantages of the response theoretical approach for describing excitation energies using different parameterizations are discussed.
描述了一种用于推导和实现振动波函数响应函数的形式体系。该形式体系利用最近发展的多模动力学二次量子化公式，为不同类型的近似振动波函数定义非冗余参数化。推导得到的响应函数涵盖了精确态、振动自洽场态和振动组态相互作用态的情况。给出了使用四次力场的双模模型系统和甲醛的线性响应函数及响应激发能的示例计算。讨论了使用不同参数化描述激发能的响应理论方法的优缺点。
