Surface–Bulk Vibrational Correlation Spectroscopy

Homo- and heterospectral correlation analysis are powerful methods for investigating the effects of external influences on the spectra acquired using distinct and complementary techniques. Nonlinear vibrational spectroscopy is a selective and sensitive probe of surface structure changes, as bulk mol...

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Bibliographic Details
Published in:Analytical chemistry (Washington) 2016-05, Vol.88 (9), p.4682-4691
Main Authors: Roy, Sandra, Covert, Paul A, Jarisz, Tasha A, Chan, Chantelle, Hore, Dennis K
Format: Article
Language:English
Subjects:
Adsorption
Analytical chemistry
Blinds
Correlation analysis
Ethyl alcohol
Experiments
Infrared absorption
Molecules
Scattering
Spectroscopy
Spectrum analysis
Surface chemistry
Vibration
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Summary:Homo- and heterospectral correlation analysis are powerful methods for investigating the effects of external influences on the spectra acquired using distinct and complementary techniques. Nonlinear vibrational spectroscopy is a selective and sensitive probe of surface structure changes, as bulk molecules are excluded on the basis of symmetry. However, as a result of this exquisite specificity, it is blind to changes that may be occurring in the solution. We demonstrate that correlation analysis between surface-specific techniques and bulk probes such as infrared absorption or Raman scattering may be used to reveal additional details of the adsorption process. Using the adsorption of water and ethanol binary mixtures as an example, we illustrate that this provides support for a competitive binding model and adds new insight into a dimer-to-bilayer transition proposed from previous experiments and simulations.
ISSN:0003-2700
1520-6882
DOI:10.1021/acs.analchem.5b04544