December 28, 2011
Journal Article

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

Abstract

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.

Revised: January 9, 2012 | Published: December 28, 2011

Citation

Velarde Ruiz Esparza L.A., X. Zhang, Z. Lu, A.G. Joly, Z. Wang, and H. Wang. 2011. Communication: Spectroscopic phase and lineshapes in high-resolution broadband sum frequency vibrational spectroscopy: Resolving interfacial inhomogeneities of "identical molecular groups." Journal of Chemical Physics 135, no. 24:Article No. 241102. PNNL-SA-83817. doi:10.1063/1.3675629