Parkhill, John AnthonyRappoport, DmitrijAspuru-Guzik, Alan2012-03-142011Parkhill, 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): 1849–1854.1948-7185http://nrs.harvard.edu/urn-3:HUL.InstRepos:8365121We 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.en-USTDDFTCARSRamanchemical enhancementJournal Article2012-03-1410.1021/jz2005573