论文标题

非绝热模型中多维电子光谱的振动响应函数

Vibrational response functions for multidimensional electronic spectroscopy in non-adiabatic models

论文作者

Troiani, Filippo

论文摘要

核和电子动力学的相互作用表征了各种分子和固态系统的多维电子光谱。从理论上讲,这种相互作用的可观察效应可以通过响应函数来解释。在这里,我们报告了与一类模型系统相对应的响应函数的分析表达式。这些特征在于,具有绝热电子状态与振动的自由度之间的耦合,从而导致相应的谐波振荡器的线性位移,以及在绝症对之间的非绝热耦合。为了得出线性响应函数,我们首先执行相关繁殖器相对于哈密顿式的非绝热成分的dyson扩展,然后在给定交互时间的位移中得出并扩展了传播器的位移,并最终为时间积分提供了分析表达式,从而为线性响应贡献了不同的贡献。然后将该方法应用于描述不同物理过程的三阶响应函数的推导:基态漂白,刺激的发射,激发状态吸收和双重量子相干性。在戴森(Dyson)扩展中最多获得第六阶的结果与响应函数的独立数值计算之间的比较为少数代表性的情况提供了串联收敛的证据。

The interplay of nuclear and electronic dynamics characterizes the multi-dimensional electronic spectra of various molecular and solid-state systems. Theoretically, the observable effect of such interplay can be accounted for by response functions. Here, we report analytical expressions for the response functions corresponding to a class of model systems. These are characterized by the coupling between the diabatic electronic states and the vibrational degrees of freedom resulting in linear displacements of the corresponding harmonic oscillators, and by nonadiabatic couplings between pairs of diabatic states. In order to derive the linear response functions, we first perform the Dyson expansion of the relevant propagators with respect to the nonadiabatic component of the Hamiltonian, then derive and expand with respect to the displacements the propagators at given interaction times, and finally provide analytical expressions for the time integrals that lead to the different contributions to the linear response function. The approach is then applied to the derivation of third-order response functions describing different physical processes: ground state bleaching, stimulated emission, excited state absorption and double quantum coherence. Comparisons between the results obtained up to sixth order in the Dyson expansion and independent numerical calculation of the response functions provide an evidence of the series convergence in a few representative cases.

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