The dependence of the transition dipole moment on nuclear coordinates gives rise to non-Condon interaction, signaling that the adiabatic Herzberg-Teller vibronic coupling should be considered. This coupling manifests itself in linear spectroscopy through the breakdown of the mirror image symmetry between the absorption and emission spectra. The stronger the non-Condon interaction, the more pronounced is the absorption-emission asymmetry. A nuclear exponential function is used as a simple model to represent the electronic transition dipole moment, the purpose of which is to avoid the use of eigenstate- approach, convergence issues, and finally be able to extend its applicability to nonlinear spectroscopy inexpensively while accounting for linear and nonlinear non-Condon effects (Herzberg-Teller vibronic coupling). The non-Condon effects on linear and nonlinear spectroscopic signals (e.g. 2-pulse photon echo) are examined. Closed-form expressions of the non-Condon electronic transition dipole moment time correlation functions, accounting for Herzberg-Teller vibronic coupling effects, are derived. It is shown that nonlinear optical signals in time domain such as 2-pulse photon echo signal, conspicuously reflects the degree of the non-Condon interaction (mostly constructive interference in this work) despite the inhomogeneous broadening disguising the homogeneous structural aspects of the molecular system of interest. As such, this study should be useful in relation to extracting structural and dynamical information of condensed molecular systems. Model calculations of absorption and emission spectra and 2-pulse photon echo signals of Herzberg-Teller vibronically coupled systems are presented. The method presented here seems to more efficient computationally, fast and stable compared to the methods which involve perturbation theory and eigenstate expansion.

跃迁偶极矩对核坐标的依赖性导致非康登相互作用，表明应考虑绝热的赫兹伯格-泰勒振动耦合。这种耦合通过吸收光谱和发射光谱之间镜像对称性的破坏在线性光谱中表现出来。非密码子相互作用越强，吸收-发射不对称性就越明显。核指数函数用作表示电子跃迁偶极矩的简单模型，其目的是避免使用本征态方法，会聚问题，并最终能够廉价地将其适用性扩展到非线性光谱学，同时考虑到线性和非线性非康登效应（Herzberg-Teller振动耦合）。研究了线性和非线性光谱信号（例如2脉冲光子回波）的非康登效应。推导了非孔顿电子跃迁偶极矩时间相关函数的闭式表达式，说明了Herzberg-Teller振动耦合效应。结果表明，时域中的非线性光信号，如二脉冲光子回波信号，尽管掩盖了目标分子系统的均质结构方面不均匀地扩展，但仍显着反映了非孔顿相互作用的程度（在这项工作中主要是相长干涉）。因此，这项研究对于提取缩合分子系统的结构和动力学信息应该是有用的。给出了Herzberg-Teller振动耦合系统吸收和发射光谱以及2脉冲光子回波信号的模型计算。与涉及扰动理论和本征态扩展的方法相比，此处介绍的方法似乎在计算上更高效，更快速且更稳定。这项研究对于提取缩合分子系统的结构和动力学信息应该是有用的。给出了Herzberg-Teller振动耦合系统吸收和发射光谱以及2脉冲光子回波信号的模型计算。与涉及扰动理论和本征态扩展的方法相比，此处介绍的方法似乎在计算上更高效，更快速且更稳定。这项研究对于提取缩合分子系统的结构和动力学信息应该是有用的。给出了Herzberg-Teller振动耦合系统吸收和发射光谱以及2脉冲光子回波信号的模型计算。与涉及扰动理论和本征态扩展的方法相比，此处介绍的方法似乎在计算上更高效，更快速且更稳定。