Surface-Enhanced Femtosecond Stimulated Raman Spectroscopy.

Surface-enhanced Raman spectroscopy (SERS) and femtosecond stimulated Raman spectroscopy (FSRS) have revolutionized the Raman spectroscopy field. SERS provides spectroscopic detection of single molecules, and FSRS enables the acquisition of Raman spectra on the ultrafast time scale of molecular motion. Here, we present the first successful combination of these two techniques, demonstrating surface-enhanced femtosecond stimulated Raman spectroscopy (SE-FSRS) using gold nanoantennas with embedded reporter molecules. Using a picosecond Raman and femtosecond probe pulse, the time- and ensemble-averaged enhancement factor is estimated to be in the range of 10(4)-10(6). We report the line shapes, power dependence, and magnitude of the SE-FSRS signal and discuss contributions to sample degradation on the minute time scale. With these first successful proof-of-principle experiments, time-resolved SE-FSRS techniques can now be rationally attempted with the goals of investigating the dynamics of plasmonic materials as well as examining the contributions of environmental heterogeneities by probing more homogeneous molecular subsets.

[1]  S. Cronin,et al.  Plasmon resonant enhancement of photocatalytic water splitting under visible illumination. , 2011, Nano letters.

[2]  Mark C. Hersam,et al.  Improved Monodispersity of Plasmonic Nanoantennas via Centrifugal Processing , 2011 .

[3]  S. Schlücker,et al.  Surface Enhancement in Femtosecond Stimulated Raman Scattering , 2010 .

[4]  George C Schatz,et al.  Structure-activity relationships in gold nanoparticle dimers and trimers for surface-enhanced Raman spectroscopy. , 2010, Journal of the American Chemical Society.

[5]  M. Wasielewski,et al.  Interrogating the Intramolecular Charge-Transfer State of a Julolidine−Anthracene Donor−Acceptor Molecule with Femtosecond Stimulated Raman Spectroscopy , 2010 .

[6]  R. Mathies,et al.  Mapping GFP structure evolution during proton transfer with femtosecond Raman spectroscopy , 2009, Nature.

[7]  R. Mathies,et al.  Probing interfacial electron transfer in coumarin 343 sensitized TiO2 nanoparticles with femtosecond stimulated Raman. , 2009, Journal of the American Chemical Society.

[8]  Richard A. Mathies,et al.  Ultrafast excited-state isomerization in phytochrome revealed by femtosecond stimulated Raman spectroscopy , 2009, Proceedings of the National Academy of Sciences.

[9]  K. Catchpole,et al.  Plasmonic solar cells. , 2008, Optics express.

[10]  R. Mathies,et al.  Origin of negative and dispersive features in anti-Stokes and resonance femtosecond stimulated Raman spectroscopy. , 2008, The Journal of chemical physics.

[11]  B. Bales,et al.  Nitroxide spin exchange due to re-encounter collisions in a series of n-alkanes. , 2008, The Journal of chemical physics.

[12]  Dana D. Dlott,et al.  Measurement of the Distribution of Site Enhancements in Surface-Enhanced Raman Scattering , 2008, Science.

[13]  N. Shah,et al.  Surface-enhanced Raman spectroscopy. , 2008, Annual review of analytical chemistry.

[14]  Zhigang Sun,et al.  Quantum theory of (femtosecond) time-resolved stimulated Raman scattering. , 2008, The Journal of chemical physics.

[15]  Carsten Rockstuhl,et al.  A plasmonic photocatalyst consisting of silver nanoparticles embedded in titanium dioxide. , 2008, Journal of the American Chemical Society.

[16]  R. Mathies,et al.  Femtosecond stimulated Raman spectroscopy. , 2007, Annual review of physical chemistry.

[17]  W. Schreier,et al.  The photochemistry of o-nitrobenzaldehyde as seen by femtosecond vibrational spectroscopy. , 2005, Angewandte Chemie.

[18]  R. Mathies,et al.  Structural Observation of the Primary Isomerization in Vision with Femtosecond-Stimulated Raman , 2005, Science.

[19]  Richard A Mathies,et al.  Femtosecond broadband stimulated Raman spectroscopy: Apparatus and methods. , 2004, The Review of scientific instruments.

[20]  S. Kawata,et al.  Local enhancement of coherent anti-Stokes Raman scattering by isolated gold nanoparticles , 2003 .

[21]  H. Hashimoto,et al.  Vibrational relaxation of the 2 A g − excited state in all- trans -β-carotene obtained by femtosecond time-resolved Raman spectroscopy , 2001 .

[22]  Wolfgang Kiefer,et al.  Experimental observation of surface-enhanced coherent anti-Stokes Raman scattering , 1994 .

[23]  J. J. McMahon,et al.  Surface enhanced raman scattering and photodimerization of pyridyl-substituted ethylenes at a silver electrode surface , 1985 .

[24]  R. Fortenberry.  Surface Coherent Anti-Stokes Raman Spectroscopy , 1985 .

[25]  Milton Kerker,et al.  Surface enhancement of coherent anti-Stokes Raman scattering by colloidal spheres , 1984 .

[26]  C. Shank,et al.  Surface vibrational spectroscopy using stimulated Raman scattering , 1979 .

[27]  J. M. Worlock,et al.  Surface picosecond raman gain spectroscopy of a cyanide monolayer on silver , 1979 .

[28]  W. Tolles,et al.  A Review of the Theory and Application of Coherent Anti-Stokes Raman Spectroscopy (CARS) , 1977 .