title: Surface-Bulk Vibrational Correlation Spectroscopy.
abstract: 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.
authors.affiliation: Department of Chemistry, University of Victoria , Victoria, British Columbia V8W 3V6, Canada.
authors.forename: Sandra
authors.initials: S
authors.lastname: Roy
authors.affiliation: Department of Chemistry, University of Victoria , Victoria, British Columbia V8W 3V6, Canada.
authors.forename: Paul A
authors.initials: PA
authors.lastname: Covert
authors.affiliation: Department of Chemistry, University of Victoria , Victoria, British Columbia V8W 3V6, Canada.
authors.forename: Tasha A
authors.initials: TA
authors.lastname: Jarisz
authors.affiliation: Department of Chemistry, University of Victoria , Victoria, British Columbia V8W 3V6, Canada.
authors.forename: Chantelle
authors.initials: C
authors.lastname: Chan
authors.affiliation: Department of Chemistry, University of Victoria , Victoria, British Columbia V8W 3V6, Canada.
authors.forename: Dennis K
authors.initials: DK
authors.lastname: Hore