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Two-Dimensional Electronic–Vibrational Spectroscopy Reveals Cross-Correlation between Solvation Dynamics and Vibrational Spectral Diffusion
The Journal of Physical Chemistry B ( IF 2.8 ) Pub Date : 2020-11-29 , DOI: 10.1021/acs.jpcb.0c08959
Minhaeng Cho 1, 2 , Graham R. Fleming 3, 4, 5
Affiliation  

Two-dimensional electronic–vibrational spectroscopy (2DEVS) is a useful technique for studying the structure and dynamics of photoexcited molecules via monitoring of the vibrational spectrum in real-time. However, quantitative modeling or prediction of experimental spectra has been hampered by the lack of a firm theoretical basis for this quantity. Here, we develop a useful theory of 2DEVS and show that the time-dependent line shape of the 2DEVS spectrum provides invaluable information on the cross-correlation function of the solvation dynamics and vibrational spectral diffusion. The center and nodal line slopes of each 2DEVS peak are determined by the associated cross-electronic–vibrational frequency–frequency correlation function, which is shown to be related to the intermolecular interactions and vibrational anharmonicities. The present theory of 2DEVS would thus be of use for a refined understanding of the 2DEVS spectra of reactive chemical and biological systems. We anticipate that further development of the expressions developed here will illuminate the application of 2DEVS studies of vibronically induced energy and electron transfer in functional materials.

中文翻译:

二维电子振动光谱揭示了溶剂化动力学与振动光谱扩散之间的互相关性

二维电子振动光谱法(2DEVS)是一种通过实时监测振动光谱研究光激发分子的结构和动力学的有用技术。但是,由于缺乏可靠的理论依据,因此无法对实验光谱进行定量建模或预测。在这里,我们发展了2DEVS的有用理论,并证明了2DEVS谱的时变线形提供了关于溶剂化动力学和振动谱扩散的互相关函数的宝贵信息。每个2DEVS峰的中心线和节点线斜率由相关的跨电子-振动频率-频率相关函数确定,该函数与分子间相互作用和振动非谐性有关。因此,2DEVS的当前理论将用于对反应性化学和生物系统的2DEVS光谱进行精细的理解。我们预期,此处开发的表达式的进一步发展将阐明2DEVS在功能性材料中进行玻璃纤维诱导的能量和电子转移的研究的应用。
更新日期:2020-12-10
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