# Modeling Coherent Anti-Stokes Raman Scattering with Time-Dependent Density Functional Theory: Vacuum and Surface Enhancement

 Title: Modeling Coherent Anti-Stokes Raman Scattering with Time-Dependent Density Functional Theory: Vacuum and Surface Enhancement Author: Parkhill, John Anthony; Rappoport, Dmitrij; Aspuru-Guzik, Alan Note: Order does not necessarily reflect citation order of authors. Citation: Parkhill, John A., Dmitrij Rappoport, and Alan Aspuru-Guzik. 2011. Modeling coherent anti-stokes raman scattering with time-dependent density functional theory: Vacuum and surface enhancement. Journal of Physical Chemistry Letters 2(15): 1849–1854. Full Text & Related Files: AG_Modeling_Coherent.pdf (397.3Kb; PDF) Abstract: We present the first density functional simulations of coherent anti-Stokes Raman scattering (CARS) and an analysis of the chemical effects upon binding to a metal surface. Spectra are obtained from first-principles electronic structure calculations and are compared with available experiments and previously available theoretical results following from Hartree–Fock polarizability derivatives. A first approximation to the nonresonant portion of the CARS signal is also explored. We examine the silver pyridine cluster models of the surface chemical signal enhancement, previously introduced for surface-enhanced Raman scattering. Chemical resonant intensity enhancements of roughly $$10^2$$ are found for several model clusters. The prospects of realizing further enhancement of CARS signal with metal surfaces is discussed in light of the predicted chemical enhancements. Published Version: doi:10.1021/jz2005573 Terms of Use: This article is made available under the terms and conditions applicable to Open Access Policy Articles, as set forth at http://nrs.harvard.edu/urn-3:HUL.InstRepos:dash.current.terms-of-use#OAP Citable link to this page: http://nrs.harvard.edu/urn-3:HUL.InstRepos:8365121

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Peer reviewed scholarly articles from the Faculty of Arts and Sciences of Harvard University