Determining the Orientation and Vibronic Couplings between Electronic and Vibrational Coordinates with Polarization-Selective 2D Vibrational-Electronic Spectroscopy.
Determining the Orientation and Vibronic Couplings between Electronic and Vibrational Coordinates with Polarization-Selective 2D Vibrational-Electronic Spectroscopy.
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使用偏振选择二维振动电子光谱确定电子坐标和振动坐标之间的方向和振动耦合。
DOI：
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发表时间：
2020
影响因子：
5.7
通讯作者：
M. Khalil
中科院分区：
文献类型：
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作者：
Zachary W. Fox;Tyler J Blair;M. Khalil
我们通过实验证明了在过渡金属混合价配合物上的偏振选择性二维振动电子（VE）光谱，其中氰化物拉伸振动与金属到金属的电荷转移跃迁相耦合。平行和交叉极化二维VE谱的同时拟合量化了电荷转移跃迁和三种耦合氰化物拉伸振动之间的相对振动耦合强度和角度。特别是，我们发现桥接振动调节过渡金属中心之间的距离，其方向几乎平行于电荷转移轴，并且与电子跃迁的耦合强度是径向振动的9倍，径向振动的方向几乎垂直于电荷转移轴。该实验的结果使我们能够将光谱观测到的振动坐标映射到分子框架上，为在飞秒时间尺度上空间解析振动能量传递提供了一种通用方法。
We experimentally demonstrate polarization-selective 2D vibrational-electronic (VE) spectroscopy on a transition metal mixed-valence complex where the cyanide stretching vibrations are coupled to the metal-to-metal charge transfer transition. A simultaneous fitting of the parallel and crossed polarized 2D VE spectra quantifies the relative vibronic coupling strengths and angles between the charge transfer transition and three coupled cyanide stretching vibrations in a mode-specific manner. In particular, we find that the bridging vibration, which modulates the distance between the transition metal centers, is oriented nearly parallel to the charge transfer axis and is nine times more strongly coupled to the electronic transition than the radial vibration, which is oriented almost perpendicular to the charge transfer axis. The results from this experiment allow us to map the spectroscopically-observed vibronic coordinates onto the molecular frame providing a general method to spatially resolve vibronic energy transfer on a femtosecond timescale.
影响因子：
16.6
作者：
Gaynor, James D.;Sandwisch, Jason;Khalil, Munira
通讯作者：
Khalil, Munira