Tony Green - A theoretical study of the sum frequency vibrational spectroscopy of the carbon tetrachloride/water interface

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  Publication Details (including relevant citation   information):

  Anthony J Green, Angela Perry, Preston B. Morre, and Brian Space,   J. Phys.: Condens. Matter 24 124108   (2012)


  Theoretical approximations to the sum frequency vibrational   spectroscopy (SFVS) of the carbon tetrachloride/water interface   are constructed using the quantum-corrected time correlation   functions (TCF) to aid in interpretation of experimental data and   to predict novel vibrational modes. Instantaneous normal mode   (INM) methods are used to characterize the observed modes leading   to the TCF signal, thus providing molecular resolution of the   vibrational lineshapes. Detailed comparisons of the theoretical   signals are made with those obtained experimentally and show   excellent agreement for the spectral peaks in the O–H stretching   region of water. An intermolecular mode, unique to the interface,   at 848 cm−1 is also identifiable, similar to the one   seen for the water/vapor interface. INM analysis reveals the   resonance is due to a wagging mode (hindered rotation) that was   previously identified (Perry et al 2005 J. Chem.   Phys. 123 144705) as localized on a single   water molecule with both hydrogens displaced normal to the   interface—generally it is found that the symmetry breaking at the   interface leads to hindered translations and rotations at   hydrophilic/hydrophobic interfaces that assume finite vibrational   frequencies due to anchoring at the aqueous interface.   Additionally, examination of the real and imaginary parts of the   theoretical SFVS spectra reveal the spectroscopic species   attributed the resonances and possible subspecies in the O–H   region; these results are consistent with extant experimental   data and associated analysis.

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