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Journal of Chemical Physics / Volume 135 / Issue 24 / COMMUNICATIONS
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J. Chem. Phys. 135, 241102 (2011); http://dx.doi.org/10.1063/1.3675629 (4 pages)

Communication: Spectroscopic phase and lineshapes in high-resolution broadband sum frequency vibrational spectroscopy: Resolving interfacial inhomogeneities of “identical” molecular groups

Luis Velarde, Xian-yi Zhang, Zhou Lu, Alan G. Joly, Zheming Wang, and Hong-fei Wang

William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, 902 Battelle Boulevard, P.O. Box 999, Richland, Washington 99352, USA

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(Received 4 November 2011; accepted 14 December 2011; published online 29 December 2011)

The ability to achieve sub-wavenumber resolution (0.6 cm−1) and a large signal-to-noise ratio in high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS) allows for the detailed SFG spectral lineshapes to be used in the unambiguous determination of fine spectral features. Changes in the structural spectroscopic phase in SFG-VS as a function of beam polarization and experimental geometry proved to be instrumental in the identification of an unexpected 2.78 ± 0.07 cm−1 spectral splitting for the two methyl groups at the vapor/dimethyl sulfoxide (DMSO, (CH3)2SO) liquid interface as well as in the determination of their orientational angles.

© 2011 American Institute of Physics

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KEYWORDS and PACS

Keywords

molecular configurations, optical frequency conversion, organic compounds, spectral line breadth, vibrational states

PACS

  • 33.70.Jg

    Line and band widths, shapes, and shifts

  • 42.65.Ky

    Frequency conversion; harmonic generation, including higher-order harmonic generation

  • 33.15.Bh

    General molecular conformation and symmetry; stereochemistry

  • 33.15.Mt

    Rotation, vibration, and vibration-rotation constants

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3675629

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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Figures (click on thumbnails to view enlargements)

FIG.1
Unsmoothed HR-BB-SFG spectra of the vapor/neat-DMSO interface for two sets of incident angles (βVIS = 65° (red) and 45° (black) with βIR = 55°) and three polarization combinations (indexed as SFG, VIS, IR). The acquisition time for each ssp spectrum is 2 min, and that for ppp and sps is 15 min. Three background-subtracted spectra were arithmetically averaged for each trace. The quartz-normalization procedure is described in the supplementary material.16

FIG.1 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.2
Expanded portion of the vapor/DMSO SFG spectra shown in Figure 1. The vertical scales are individually adjusted for better lineshape comparison. The solid lines are the results of the fitting procedure described in the text to the experimental data (dots). Linewidth narrowing is clearly evident in the ppp lineshape obtained at βVIS = 65°.

FIG.2 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

FIG.3
Resolving the orientation (θ1, θ2) of the two methyl groups in (a) is made possible by means of the structural phase in the ppp polarization, as shown in (b), for experimental configurations I and II (see text). The orientational curves in (b) were generated using a hyperpolarizability ratio (R) of 2.26, nIR ≈ nvis = nSFG = 1.478, and n′ = 1.208.7 , 16 , 20 The secβi factor in (b), where βi is the respective SFG angle, allows for the direct comparison between experimental geometries;16 (c) and (d) show the decomposed fitting Lorentzians, i.e., |χNR + ∑qAq/(ωIR − ωq + iΓq)|2 (see Table 1), for the ppp spectra in experimental configurations I and II. (e) and (f) show the intensity-scaled SFG lineshapes and how interference with a non-resonant background χNR is necessary to reproduce the experimental lineshapes, particularly the baseline dips in configuration I, which are unique for the opposite phase double-peak scenario.

FIG.3 Download High Resolution Image (.zip file) | Export Figure to PowerPoint

Supplemental Files (EPAPS)

Tables

Table I. Parameters derived from the simultaneous fit.16

View Table

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