Heterodyned 3D IR spectroscopy
Heterodyned 3D IR spectroscopy
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DOI：
10.1016/j.chemphys.2007.06.010
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发表时间：
2007-11-15
期刊：
影响因子：
2.3
通讯作者：
Zanni, Martin T.
中科院分区：
文献类型：
--
作者：
Ding, Feng;Zanni, Martin T.
外差3D红外光谱报告的三个模型化合物：W（CO）6，叠氮化物在离子玻璃，和铱金属二羰基。使用五阶脉冲序列生成3D光谱，该五阶脉冲序列的信号沿沿着三个单独的相干演化时间进行傅立叶变换。由于脉冲序列将静态振动频率重相为光子回波，因此3D IR光谱对于均匀加宽的振动模式表现出球形特征，并且对于非均匀加宽的系统表现出细长的雪茄状特征。3D频谱可以被可视化为在泛音和组合频带频率处出现的一系列平面。每个平面包含2D相关图。在典型的2D IR光谱中，对角峰和交叉峰都出现在相同的相关图中，但在3D IR光谱中，对角峰和交叉峰被分离到不同的2D平面中，大大提高了光谱分辨率。三维红外光谱的模拟和未来的改进技术进行了讨论。这项工作表明，增加控制振动相干增强多维红外光谱的分辨率和信息内容。(C)2007 Elsevier B.V.保留所有权利。
Heterodyned 3D IR spectra are reported for three model compounds: W(CO)6, azide in an ionic glass, and an iridium metal dicarbonyl. The 3D spectra are generated using a fifth-order pulse sequence whose signal is Fourier transformed along three separate coherence evolution times. Because the pulse sequence rephases static vibrational frequencies into a photon echo, the 3D IR spectra exhibit spherical features for homogeneously broadened vibrational modes and elongated cigar-like features for inhomogeneously broadened systems. The 3D spectra can be visualized as a series of planes appearing at the overtone and combination band frequencies. Each plane contains a 2D correlation map. In a typical 2D IR spectrum, both diagonal peaks and cross peaks appear in the same correlation map, but in 3D IR spectroscopy the diagonal and cross peaks are separated into different 2D planes, greatly improving the spectral resolution. Simulations of the 3D IR spectra are also presented and future improvements to the technique are discussed. This work demonstrates that increased control over vibrational coherences enhances the resolution and information content of multidimensional infrared spectroscopies. (C) 2007 Elsevier B.V. All rights reserved.