Identification of overlapping features in the sum frequency generation vibrational spectra of air/ethanol interface

The stretching vibrations of the –CH3 and –CH2– groups not only overlap but also interfere with each other in the Sum-Frequency Generation (SFG) vibrational spectra of the air/ethanol interface. Using deuterated ethanol samples, i.e., CH3CD2OH and CD3CH2OH, the C–H stretching vibrational modes are clearly assigned for the SFG vibrational spectra of their air/liquid interfaces according to the polarization selection rules. It is found that the CH3-ss and CH2-ss modes overlap in the ∼2875 cm−1 peak, the CH3-as and CH2-ss-Fermi modes overlap in the ∼2970 cm−1 peak, and the ∼2930 cm−1 peak belongs to the CH3-ss-Fermi mode, respectively.

[1]  D. I. Bower,et al.  The vibrational spectroscopy of polymers: Main index , 1989 .

[2]  G. Herzberg,et al.  Molecular Spectra and Molecular Structure , 1992 .

[3]  Samuel Krimm,et al.  Vibrational spectra in the CH stretching region and the structure of the polymethylene chain , 1978 .

[4]  K. Eisenthal,et al.  Liquid Interfaces Probed by Second-Harmonic and Sum-Frequency Spectroscopy. , 1996, Chemical reviews.

[5]  J. E. Griffiths,et al.  Relative and Absolute Raman Scattering Cross Sections in Liquids , 1972 .

[6]  T. Kitagawa,et al.  Behavior of ethanol in various binary solutions: difference Raman spectroscopy on the C-H stretching vibrations , 1987 .

[7]  S. Mukamel,et al.  Two-Dimensional Raman Echoes: Femtosecond View of Molecular Structure and Vibrational Coherence , 1999 .

[8]  R. Hochstrasser,et al.  Two-dimensional IR spectroscopy can be designed to eliminate the diagonal peaks and expose only the crosspeaks needed for structure determination , 2001, Proceedings of the National Academy of Sciences of the United States of America.

[9]  R. G. Snyder,et al.  Band structure in the C–H stretching region of the Raman spectrum of the extended polymethylene chain: Influence of Fermi resonance , 1979 .

[10]  W. Gan,et al.  Vibrational Polarization Spectroscopy of CH Stretching Modes of the Methylene Group at the Vapor/Liquid Interfaces with Sum Frequency Generation , 2004 .

[11]  L. J. Bellamy The infra-red spectra of complex molecules , 1962 .

[12]  S. Mukamel,et al.  Two-dimensional femtosecond vibrational spectroscopy of liquids , 1993 .

[13]  G. Somorjai,et al.  Polar ordering at the liquid-vapor interface of n-alcohols (C1-C8) , 1995 .

[14]  W. Gan,et al.  Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS) , 2005 .

[15]  D. Dlott Vibrational energy redistribution in polyatomic liquids: 3D infrared–Raman spectroscopy , 2001 .

[16]  Jung Y. Huang,et al.  Sum Frequency Vibrational Spectroscopy of the Liquid-Air Interface of Aqueous Solutions of Ethanol in the OH Region , 2001 .

[17]  W. Gan,et al.  Orientation and Motion of Water Molecules at Air/Water Interface , 2005, cond-mat/0508525.

[18]  Isao Noda,et al.  Advances in two-dimensional correlation spectroscopy , 2004 .

[19]  Paulo B. Miranda,et al.  Mapping molecular orientation and conformation at interfaces by surface nonlinear optics , 1999 .

[20]  W. Gan,et al.  Polarization and experimental configuration analyses of sum frequency generation vibrational spectra, structure, and orientational motion of the air/water interface. , 2005, The Journal of chemical physics.

[21]  J. Chalmers,et al.  Handbook of vibrational spectroscopy , 2002 .

[22]  Huang,et al.  Nonlinear optical studies of the pure liquid/vapor interface: Vibrational spectra and polar ordering. , 1991, Physical review letters.

[23]  A. E. Martin,et al.  Investigations of Infra-Red Spectra. Absorption of the CH$_{2}$ Group in the Region of 3$ \mu $ , 1938 .

[24]  Ji-Xin Cheng,et al.  Ordering of water molecules between phospholipid bilayers visualized by coherent anti-Stokes Raman scattering microscopy , 2003, Proceedings of the National Academy of Sciences of the United States of America.

[25]  C. Rauscher,et al.  Time-resolved infrared spectroscopy of ethanol monomers in liquid solution: molecular reorientation and energy relaxation times , 1997 .

[26]  W. Gan,et al.  C-H stretching vibrations of methyl, methylene and methine groups at the vapor/alcohol (N = 1-8) interfaces. , 2005, The journal of physical chemistry. B.

[27]  Y. Shindo,et al.  NMR and FT-IR Studies of Hydrogen Bonds in Ethanol-Water Mixtures , 1995 .

[28]  Dana D. Dlott,et al.  Watching Vibrational Energy Transfer in Liquids with Atomic Spatial Resolution , 2002, Science.

[29]  J. Sung,et al.  Surfaces of alcohol-water mixtures studied by sum-frequency generation vibrational spectroscopy. , 2005, The journal of physical chemistry. B.