title: Surface-Enhanced Spectroscopy for Higher-Order Light Scattering: A Combined Experimental and Theoretical Study of Second Hyper-Raman Scattering.
abstract: Motivated to explore the ultimate limits of surface-enhanced nonlinear spectroscopies, we report on the first observation of molecular second hyper-Raman scattering with the aid of surface enhancement and provide a new theoretical framework for first-principles calculations of the second hyper-Raman effect. Second hyper-Raman enhancement factors, determined to be a minimum of 10(5) times stronger than those in Raman scattering, demonstrate a clear trend toward larger enhancements for nonlinear phenomena, and the nearly quantitative agreement between simulation and experiment provides a unique spectroscopic window into higher-order molecular responses.
authors.affiliation: Department of Chemistry, University of Tennessee , Knoxville, Tennessee 37996, United States.
authors.forename: Philip D
authors.initials: PD
authors.lastname: Simmons
authors.affiliation: Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Hubert K
authors.initials: HK
authors.lastname: Turley
authors.affiliation: Department of Chemistry, Pennsylvania State University , University Park, Pennsylvania 16802, United States.
authors.forename: Daniel W
authors.initials: DW
authors.lastname: Silverstein
authors.affiliation: Department of Chemistry, Pennsylvania State University , University Park, Pennsylvania 16802, United States.
authors.forename: Lasse
authors.initials: L
authors.lastname: Jensen
authors.affiliation: Department of Chemistry and Biochemistry, University of Notre Dame , Notre Dame, Indiana 46556, United States.
authors.forename: Jon P
authors.initials: JP
authors.lastname: Camden
keywords: first-principles theory; nonlinear spectroscopy; surface-enhanced Raman scattering