Hniopek Julian, Müller Carolin, Bocklitz Thomas, Schmitt Michael, Dietzek Benjamin, Popp Jürgen
Leibniz Institute of Photonic Technology, Albert-Einstein-Str. 9, 07745 Jena, Germany.
Friedrich Schiller University Jena, Institute of Physical Chemistry, Helmholtzweg 4, 07743 Jena, Germany.
J Phys Chem Lett. 2021 May 6;12(17):4148-4153. doi: 10.1021/acs.jpclett.1c00835. Epub 2021 Apr 23.
Here, we present, to the best of our knowledge for the first time, a systematic study of utilizing 2D correlation analysis in the field of femtosecond transient absorption (fs-TA) spectroscopy. We present that the application of 2D correlation spectroscopy (2DCOS) to fs-TA spectroscopy enables a model-free means to analyze excited state kinetics, which is demonstrated on the model system [(tbbpy)Ru(dppz)] in different solvents. We show that TA-2DCOS is able to determine the number of processes contributing to the time-resolved spectral changes in fs-TA data sets, as well as extract the spectral response of these components. Overall, the results show that TA-2DCOS leads to the same results as obtained with methods relying on global lifetime analysis or multivariate curve resolution but without the need to specify a predetermined kinetic model. The work presented therefore highlights the potential of TA-2DCOS as a model-free approach for analyzing fs-TA spectral data sets.
在此，据我们所知，我们首次对飞秒瞬态吸收（fs-TA）光谱领域中二维相关分析的应用进行了系统研究。我们提出，将二维相关光谱（2DCOS）应用于fs-TA光谱能够提供一种无模型的方法来分析激发态动力学，这在不同溶剂中的模型体系[(tbbpy)Ru(dppz)]上得到了验证。我们表明，TA-2DCOS能够确定对fs-TA数据集中时间分辨光谱变化有贡献的过程数量，并提取这些组分的光谱响应。总体而言，结果表明TA-2DCOS与依赖全局寿命分析或多元曲线分辨的方法得到的结果相同，但无需指定预先确定的动力学模型。因此，所展示的这项工作突出了TA-2DCOS作为一种分析fs-TA光谱数据集的无模型方法的潜力。
