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

Journal Article · Wed Dec 28 04:00:00 EST 2011 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3675629· OSTI ID:1033066

Velarde Ruiz Esparza, Luis A; Zhang, Xianyi; Lu, Zhou; Joly, Alan G; Wang, Zheming; Wang, Hongfei

The ability to achieve sub-wavenumber resolution (0.6 cm-1) and large signal-to-noise ratios 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 two methyl groups at the vapor/dimethyl sulfoxide liquid interface, as well as in the determination of their orientational angles.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1033066
• Report Number(s): PNNL-SA-83817; 46004
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 135; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Environmental Molecular Sciences Laboratory
GEOMETRY
High-resolution
broadband laser spectroscopy
dimethyl sulfoxide
liquid interfaces
vibrational spectroscopy
sum-frequency generation
POLARIZATION
RESOLUTION
SIGNAL-TO-NOISE RATIO
SPECTROSCOPY
SULFOXIDES