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Vibrational correlation between conjugated carbonyl and diazo modes studied by single- and dual-frequency two-dimensional infrared spectroscopy
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https://doi.org/10.1016/j.chemphys.2013.02.010Abstract
We have applied infrared three-pulse photon echo and single- and dual-frequency 2D IR spectroscopy to the ester C=O and diazo N=N stretching modes in ethyl diazoacetate (EDA), and investigated their vibrational frequency fluctuations and correlation. The two modes exhibit different vibrational dynamics and 2D lineshape, which are well simulated by frequency-frequency correlation functions (FFCFs) with two decaying components. Although the FT IR spectrum shows a single C=O band, absolute magnitude 2D IR nonrephasing spectrum displays spectral signatures supporting the presence of cis and trans conformations. The cross-peak inclined toward the anti-diagonal in the dual-frequency 2D IR spectrum, indicating that the frequency fluctuations of the two modes are anticorrelated. This behavior is attributed to anti-correlated change in the bond orders when solvent and structural fluctuations causes EDA to adopt a different mixture of the two dominant resonance structures. The effects of cross FFCF on the cross-peak line shape are discussed. © 2013 Elsevier B.V. All rights reserved.
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