Resolving Two Closely Overlapping -CN Vibrations and Structure in the Langmuir Monolayer of the Long-Chain Nonadecanenitrile by Polarization Sum Frequency Generation Vibrational Spectroscopy
Polarization sum frequency generation vibrational spectra (SFG-VS) reveals that there are two distinctively different but closely overlapping -CN vibrations at 2244.5 cm{sup -1} and 2251.1 cm{sup -1}, respectively, in the Langmuir monolayer of the long-chain nonadecanenitrile (C18CN, CH{sub 3}(CH{sub 2}){sub 17}CN, or C18CN)at the air/water interface. The blue shifted -CN groups at 2251.1 cm{sup -1} peak is about 1.8 times broader than that of the 2244.5 cm{sup -1}. Both the spectral shift and spectral width are consistent with the picture that this blue shifted peak corresponds to the solvated -CN group; while the 2244.5 cm{sup -1} peak is the signature of the less solvated -CN group. Polarization dependence of these two peaks further suggest that the -CN group corresponding to the 2251.1 cm{sup -1} peak is tilted with an average angle of 50{sup o} from interface normal, where that to the 2244.5 cm{sup -1} peak is tilted with an angle around 67{sup o}. The relative population for the -CN groups corresponding to the 2251.1 cm{sup -1} peak is about three times of that of the 2244.5 cm{sup -1} peak. These results suggest that the -CN head groups in the C18CN Langmuir monolayer are not aligned uniformly at slightly different depth, in order to avoid the strong repulsive forces between the strong -CN dipoles. The SFG-VS spectra of the O-H stretches at C18CN Langmuir monolayer is similar to those of the 4''-n-pentyl-4-cyano-p-terphenyl (5CT) monolayer, indicating complete exclusion of the water molecules from the C18CN Langmuir monolayer, but significantly different from those of the 4''-n-octyl-4-p-cyanobiphenyl (8CB) monolayer, as well as those of the air/acetonitrile aqueous solution interface. Different from previous held understandings, these results suggest that the structure of the insoluble long-chain C18CN Langmuir monolayer is significantly different from that of the Gibbs adsorption layer of the short chain soluble acetonitrile or propanenitrile aqueous solution surfaces. These observations not only shed new light on understanding the detailed structure and interactions in the molecular monolayer and films, but also suggest the importance of the polarization and spectral resolution in the SFG studies.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1034575
- Report Number(s):
- PNNL-SA-83653; 46004; TRN: US201203%%628
- Journal Information:
- Journal of Physical Chemistry C, Vol. 116, Issue 4; ISSN 1932-7447
- Country of Publication:
- United States
- Language:
- English
Similar Records
Unique determination of the -CN group tilt angle in Langmuir monolayers using sum-frequency polarization null angle and phase
Homogeneous and inhomogeneous broadenings and the Voigt line shapes in the phase-resolved and intensity sum-frequency generation vibrational spectroscopy
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ACETONITRILE
ADSORPTION
AQUEOUS SOLUTIONS
CHAINS
DIPOLES
POLARIZATION
RESOLUTION
SPECTRA
SPECTRAL SHIFT
SPECTROSCOPY
WATER
Surface
vibratiobnal spectroscopy
Sum-Frequency Generation
Langmuir monolayer
nonadecanenitrile
Environmental Molecular Sciences Laboratory