Campus Units

Ames Laboratory, Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

4-13-2012

Journal or Book Title

Analytical Chemistry

Volume

84

Issue

10

First Page

4300

Last Page

4306

DOI

10.1021/ac203355a

Abstract

Total internal reflection (TIR) Raman and reflectivity spectra were collected for nonresonant analytes as a function of incident angle at sapphire or sapphire/smooth 50 nm gold interfaces using 785 nm excitation. For both interfaces, the Raman signal as a function of incident angle is well-modeled by the calculated interfacial mean square electric field (MSEF) relative to the incident field times the thickness of the layer being probed in the Raman measurement (DRS). The Raman scatter was reproducibly enhanced at the interface containing a gold film relative to the sapphire interface by a factor of 4.3−4.6 for aqueous pyridine or 2.2−3.7 for neat nitrobenzene, depending on the analyzed vibrational mode. The mechanism for the increased Raman signal is the enhanced MSEF at incident angles where propagating surface plasmons are excited in the metal film. The background from the TIR prism was reduced by 89−95% with the addition of the gold film, and the percent relative uncertainty in peak area was reduced from 15 to 1.7% for the 1347 cm−1 mode of nitrobenzene. Single monolayers of benzenethiol (S/N = 6.8) and 4-mercaptopyridine (S/N = 16.5) on gold films were measured by TIR Raman spectroscopy with 785 nm excitation (210 mW) without resonant enhancement in 1 min.

Comments

Reprinted (adapted) with permission from Analytical Chemistry, 84(10); 4300-4306. Doi: 10.1021/ac203355a. Copyright 2012 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

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