Theoretical studies of surface enhanced hyper-Raman spectroscopy: The chemical enhancement mechanism

Nicholas Valley, Lasse Jensen, Jochen Autschbach, George C. Schatz

Research output: Contribution to journalArticlepeer-review

44 Scopus citations


Hyper-Raman spectra for pyridine and pyridine on the surface of a tetrahedral 20 silver atom cluster are calculated using static hyperpolarizability derivatives obtained from time dependent density functional theory. The stability of the results with respect to choice of exchange-correlation functional and basis set is verified by comparison with experiment and with Raman spectra calculated for the same systems using the same methods. Calculated Raman spectra were found to match well with experiment and previous theoretical calculations. The calculated normal and surface enhanced hyper-Raman spectra closely match experimental results. The chemical enhancement factors for hyper-Raman are generally larger than for Raman (102 - 104 versus 101 - 102). Integrated hyper-Raman chemical enhancement factors are presented for a set of substituted pyridines. A two-state model is developed to predict these chemical enhancement factors and this was found to work well for the majority of the molecules considered, providing a rationalization for the difference between hyper-Raman and Raman enhancement factors.

Original languageEnglish (US)
Article number054103
JournalJournal of Chemical Physics
Issue number5
StatePublished - Aug 7 2010

All Science Journal Classification (ASJC) codes

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


Dive into the research topics of 'Theoretical studies of surface enhanced hyper-Raman spectroscopy: The chemical enhancement mechanism'. Together they form a unique fingerprint.

Cite this