Issue 34, 2009

Single-molecule vibrational pumping in SERS

Abstract

Single-molecule vibrational pumping in surface-enhanced Raman scattering (SERS) is demonstrated rigorously using the bi-analyte SERS method at low temperatures. These experiments reveal a systematic difference between the radiative SERS cross section estimated from the Stokes intensity and that obtained by pumping itself (from the anti-Stokes-to-Stokes ratio), the latter being always larger. This difference can only be reliably demonstrated in the single-molecule SERS regime, for it is otherwise affected by complications of the averaging (over the enhancement distribution) of the signals of several molecules. The findings in this paper highlight the limitations of the pumping cross-section, which cannot (in general) be taken as a reliable measure of the SERS cross-section itself. We provide a discussion of the main possible explanations for the systematic difference of the two estimates.

Graphical abstract: Single-molecule vibrational pumping in SERS

Article information

Article type
Paper
Submitted
06 Mar 2009
Accepted
28 May 2009
First published
29 Jun 2009

Phys. Chem. Chem. Phys., 2009,11, 7372-7380

Single-molecule vibrational pumping in SERS

C. M. Galloway, E. C. Le Ru and P. G. Etchegoin, Phys. Chem. Chem. Phys., 2009, 11, 7372 DOI: 10.1039/B904638K

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements