论文标题
绝热状态中多维电子光谱的振动响应函数:连贯的方法
Vibrational response functions for multidimensional electronic spectroscopy in the adiabatic regime: a coherent-state approach
论文作者
论文摘要
多维光谱法代表了研究核和电子动力学相互作用的特别有见地的工具,该工具在许多光物理过程和光化学反应中起着重要作用。在这里,我们提出了振动动力学的连贯状态表示以及广泛使用线性位移振荡器模型的结果响应函数的一致性。最初针对N级系统中三阶响应函数的情况得出分析表达式,并具有振荡器的基态初始化(零温度极限)。然后将结果推广到M-Ther阶响应函数的情况,并具有任意M。形式推导被翻译成简单的配方,从而可以直接从Feynman图中得出响应函数的显式分析表达式。我们进一步概括了整个初始相干状态,这些状态构成了过度的基础。这原理可以得出响应函数对振动模式的任意初始状态的依赖性,并在此处应用于热状态。最后,一种非富米顿式的方法用于在上面的表达中包括振动弛豫的效果。
Multi-dimensional spectroscopy represents a particularly insightful tool for investigating the interplay of nuclear and electronic dynamics, which plays an important role in a number of photophysical processes and photochemical reactions. Here we present a coherent state representation of the vibronic dynamics and of the resulting response functions for the widely used linearly displaced oscillator model. Analytical expressions are initially derived for the case of third-order response functions in an N-level system, with ground state initialization of the oscillator (zero-temperature limit). The results are then generalized to the case of M-th order response functions, with arbitrary M. The formal derivation is translated into a simple recipe, whereby the explicit analytical expressions of the response functions can be derived directly from the Feynman diagrams. We further generalize to the whole set of initial coherent states, which form an overcomplete basis. This allows one in principle to derive the dependence of the response functions on arbitrary initial states of the vibrational modes and is here applied to the case of thermal states. Finally, a non-Hermitian Hamiltonian approach is used to include in the above expressions the effect of vibrational relaxation.