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Title: Accurate Lineshapes from Sub-1 cm-1 Resolution Sum Frequency Generation Vibrational Spectroscopy of α-Pinene at Room Temperature

Room temperature sub-wavenumber high-resolution broadband sum frequency generation (HR-BB-SFG) spectra of the common terpene (+)-α-pinene reveal ten peaks in the C–H stretching region. The spectral resolution exceeds that of Fourier transform infrared, femtosecond stimulated Raman, and traditional BB-SFG and scanning SFG spectroscopy of the same molecule. Experiment and simulation show the spectral lineshapes to be accurate. Homogeneous vibrational decoherence lifetimes of up to 1.7 psec are assigned to specific oscillators and compare favorably to lifetimes computed from density functional tight binding molecular dynamics calculations, while phase-resolved spectra yield orientation information for them. We propose the new spectroscopy as an attractive alternative to time-resolved vibrational spectroscopy or heterodyne-detection schemes for studying vibrational energy relaxation and vibrational coherences in molecules.
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Publication Date:
OSTI Identifier:
Report Number(s):
47891; KP1704020
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry A, 119(8):1292-1302
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org:
Country of Publication:
United States
Resolution; sum; frequency; generation; vibrational; spectra; Pinene; Environmental Molecular Sciences Laboratory