Accurate Line Shapes from Sub‑1 cm–1 Resolution Sum Frequency Generation Vibrational Spectroscopy of α‑Pinene at Room Temperature
journal contributionposted on 26.02.2015, 00:00 by Amanda L. Mifflin, Luis Velarde, Junming Ho, Brian T. Psciuk, Christian F. A. Negre, Carlena J. Ebben, Mary Alice Upshur, Zhou Lu, Benjamin L. Strick, Regan J. Thomson, Victor S. Batista, Hong-Fei Wang, Franz M. Geiger
Despite the importance of terpenes in biology, the environment, and catalysis, their vibrational spectra remain unassigned. Here, we present subwavenumber high-resolution broad-band sum frequency generation (HR-BB-SFG) spectra of the common terpene (+)-α-pinene that reveal 10 peaks in the C–H stretching region at room temperature. The high spectral resolution resulted in spectra with more and better resolved spectral features than those of the Fourier transform infrared, femtosecond stimulated Raman spectra in the bulk condensed phase and those of the conventional BB-SFG and scanning SFG spectroscopy of the same molecule on a surface. Experiment and simulation show the spectral line shapes with HR-BB-SFG to be accurate. Homogeneous vibrational decoherence lifetimes of up to 1.7 ps are assigned to specific oscillators and compare favorably to lifetimes computed from density functional tight binding molecular dynamics calculations. Phase-resolved spectra provided their orientational information. We propose the new spectroscopy as an attractive alternative to time domain vibrational spectroscopy or heterodyne detection schemes for studying vibrational energy relaxation and vibrational coherences in molecules at molecular surfaces or interfaces.
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10 peaksRaman spectraorientational informationvibrational coherencesline shapesscanning SFG spectroscopy1.7 psAccurate Line Shapesheterodyne detection schemesvibrational energy relaxationHomogeneous vibrational decoherence lifetimesterpenedynamics calculationstime domain vibrational spectroscopysimulation showsurfaceRoom TemperatureDespitevibrational spectramoleculeroom temperature