title: Theoretical approach for optical response in electrochemical systems: application to electrode potential dependence of surface-enhanced Raman scattering.
abstract: We propose a theoretical approach for optical response in electrochemical systems. The fundamental equation to be solved is based on a time-dependent density functional theory in real-time and real-space in combination with its finite temperature formula treating an electrode potential. Solvation effects are evaluated by a dielectric continuum theory. The approach allows us to treat optical response in electrochemical systems at the atomistic level of theory. We have applied the method to surface-enhanced Raman scattering (SERS) of 4-mercaptopyridine on an Ag electrode surface. It is shown that the SERS intensity has a peak as a function of the electrode potential. Furthermore, the real-space computational approach facilitates visualization of variation of the SERS intensity depending on an electrode potential.
authors.affiliation: Department of Theoretical and Computational Molecular Science, Institute for Molecular Science, Okazaki 444-8585, Japan.
authors.forename: Kenji
authors.initials: K
authors.lastname: Iida
authors.affiliation: Department of Theoretical and Computational Molecular Science, Institute for Molecular Science, Okazaki 444-8585, Japan.
authors.forename: Masashi
authors.initials: M
authors.lastname: Noda
authors.affiliation: Department of Theoretical and Computational Molecular Science, Institute for Molecular Science, Okazaki 444-8585, Japan.
authors.forename: Katsuyuki
authors.initials: K
authors.lastname: Nobusada