The effect of static disorder on the center line slope in 2D electronic spectroscopy
arxiv(2023)
摘要
Two-dimensional electronic spectroscopy (2DES) is a powerful tool for
investigating the dynamics of complex systems. However, analyzing the resulting
spectra can be challenging, and thus may require the use of theoretical
modeling techniques. The center line slope (CLS) method is one of such
approaches, which aims to extract the time correlation function (TCF) from 2DES
with minimal error. Since static disorder is widely observed in complex
systems, it may be interesting to ask whether the CLS approach still work in
the presence of the static disorder. In this paper, the effect of the static
disorder on the TCF obtained through the CLS method is investigated. It is
found that the steady-state value of the CLS increases monotonically with
respect to the static disorder, which suggests that the amplitude of the static
disorder can be determined using the CLS in the long-time limit. Additionally,
as the static disorder rises, the decay rate of the CLS first decreases to a
certain value and remains at this value until the static disorder is
sufficiently large. Afterward, the CLS begins to fluctuate significantly and
thus results in obtaining the decay rate through the CLS method unreliable.
Based on these discoveries, we propose a method to fix the error and obtain the
TCF. Our findings may pave the way for obtaining reliable system-bath
information by analyzing 2DES in the practical situations.
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关键词
spectroscopy,static disorder,center line slope
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