泵浦探针光谱学中的逆问题

Photochem Pub Date : 2024-01-31 DOI:10.3390/photochem4010005
Denis S. Tikhonov, Diksha Garg, Melanie Schnell
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引用次数: 0

摘要

通过超快泵探针光谱研究,可以深入了解光物理和光化学过程的机理和时间尺度。从这些研究中提取有价值的信息,如反应中间体的寿命和相干振荡频率,是化学动力学逆问题的一个例子。本文介绍了解决这一反问题的一致方法,避免了简单最小二乘拟合可能导致不可靠结果的常见障碍。本文介绍的方法基于对强非线性参数的正则化马尔科夫链蒙特卡洛采样,从而可以直接解决难题非线性逆问题。我们将介绍实现所述拟合例程的软件,并给出其应用的数值示例。我们还将讨论关键的实验参数,如脉冲的时间重叠和交叉相关时间,以及它们与可达到的最小时间分辨率之间的联系。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Inverse Problems in Pump–Probe Spectroscopy
Ultrafast pump–probe spectroscopic studies allow for deep insights into the mechanisms and timescales of photophysical and photochemical processes. Extracting valuable information from these studies, such as reactive intermediates’ lifetimes and coherent oscillation frequencies, is an example of the inverse problems of chemical kinetics. This article describes a consistent approach for solving this inverse problem that avoids the common obstacles of simple least-squares fitting that can lead to unreliable results. The presented approach is based on the regularized Markov Chain Monte-Carlo sampling for the strongly nonlinear parameters, allowing for a straightforward solution of the ill-posed nonlinear inverse problem. The software to implement the described fitting routine is introduced and the numerical examples of its application are given. We will also touch on critical experimental parameters, such as the temporal overlap of pulses and cross-correlation time and their connection to the minimal reachable time resolution.
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CiteScore
3.60
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