arXiv subjects

P. G. Etchegoin

Publications and source records attributed to P. G. Etchegoin.

10 recordsLinked to original sources

arXiv2008

Evidence of natural isotopic distribution from single-molecule SERS

We report on the observation of the natural isotopic spread of carbon from single-molecule Surface Enhanced Raman Spectroscopy (SM-SERS). By choosing a dye molecule with a very localized Raman active vibration in a cyano bond (C$\equiv$N triple bond), we observe (in a SERS colloidal liquid) a small fraction of SM-SERS events where the frequency of the cyano mode is softened and in agreement with the effect of substituting $^{12}$C by the next most abundant $^{13}$C isotope. This example adds another demonstration of single molecule sensitivity in SERS through isotopic editing which is done, in this case, not by artificial isotopic editing but rather by nature itself. It also highlights SERS as a unique spectroscopic tool, capable of detecting an isotopic change in one atom of a single molecule.

cond-mat.soft↗

arXiv2007

Temperature-dependent Raman scattering of natural and isotopically substituted PbS

Lead sulfide is an important semiconductor that has found technological applications for over a century. Raman spectroscopy, a standard tool for the investigation and characterization of semiconductors, has limited application to this material because of the forbidden nature of its first order scattering and its opacity to visible lasers. Nevertheless, useful vibrational spectra from two-phonon processes are obtained with red lasers, probably because of a resonance in the concomitant electronic transitions. Here we report temperature dependent spectra, covering the 10-300 K range, for two samples with different sulfur isotopic compositions. The results are analyzed by comparison with ab initio calculations of the lattice dynamics of PbS and the corresponding densities of one and two-phonon states. Emphasis is placed on the analysis of the two phonon band centered at ~430 cm-1.

cond-mat.mtrl-sci↗

arXiv2006

Enhancement factor distribution around a single SERS Hot-spot and its relation to Single Molecule detection

We provide the theoretical framework to understand the phenomenology and statistics of single-molecule (SM) signals arising in Surface-Enhanced Raman Scattering (SERS) under the presence of so-called electromagnetic hot-spots (HS's). We show that most characteristics of the SM-SERS phenomenon can be tracked down to the presence of tail-like (power law) distribution of enhancements and we propose a specific model for it. We analyze, in the light of this, the phenomenology of SM-SERS and show how the different experimental manifestations of the effect reported in the literature can be analyzed and understood under a unified ``universal'' framework with a minimum set of parameters.

physics.chem-ph↗

arXiv2006

On the Experimental Estimation of Surface Enhanced Raman Scattering (SERS) Cross Sections by Vibrational Pumping

We present an in-depth analysis of the experimental estimation of cross sections in Surface Enhanced Raman Scattering (SERS) by vibrational pumping. The paper highlights the advantages and disadvantages of the technique, pinpoints the main aspects and limitations, and provides the underlying physical concepts to interpret the experimental results. Examples for several commonly used SERS probes are given, and a discussion on future possible developments is also presented.

physics.chem-ph↗

arXiv2005

A conclusive demonstration of vibrational pumping and determination of SERS cross sections

We provide conclusive demonstration of vibrational pumping under Surface Enhanced Raman Scattering (SERS) conditions by performing anti-Stokes/Stokes ratio measurements down to 10 K using dried silver colloids, the dye rhodamine 6G and 676 nm laser excitation. The method we propose allows the measurement of the SERS cross sections for different modes and the determination of the asymmetry between the anti-Stokes and Stokes SERS cross sections.

physics.chem-ph↗

arXiv2005

Temperature dependent anti-Stokes/Stokes ratios under Surface Enhanced Raman Scattering (SERS) conditions

We make systematic measurements of Raman anti-Stokes/Stokes (aS/S) ratios using two different laser excitations (514 and 633 nm) of rhodamine 6G (RH6G) on dried Ag colloids over a wide range of temperatures (100 to 350 K). We show that a temperature scan allows the separation of the contributions to the aS/S ratios from {\it resonance effects} and {\it heating/pumping}, thus decoupling the two main aspects of the problem. The temperature rise is found to be larger when employing the 633 nm laser. In addition, we find evidence for mode specific vibrational pumping at higher laser power densities. We analyze our results in the framework of ongoing discussion on laser heating/pumping under SERS conditions.

physics.chem-ph↗

arXiv2005

Bi-Analyte Surface Enhanced Raman Scattering for unambiguous evidence of single molecule detection

A method is proposed to pin down an unambiguous proof for single molecule surface enhanced Raman spectroscopy (SERS). The simultaneous use of two analyte molecules enables a clear confirmation of the single (or few) molecule nature of the signals. This method eliminates most of the uncertainties associated with low dye concentrations in previous experiments. It further shows that single-molecule signals are very common in SERS, both in liquids and on dry substrates.

physics.chem-ph↗

arXiv2005

Surface-Enhanced Raman Scattering (SERS) and Surface-Enhanced Fluorescence (SEF) in the context of modified spontaneous emission

Surface Enhanced Raman Scattering (SERS) and Surface-Enhanced Fluorescence (SEF) are studied within the framework of modified Spontaneous Emission (SE), and similarities and differences are highlighted. This description sheds new light into several aspects of the SERS electromagnetic enhancement. In addition, combined with the optical reciprocity theorem it also provides a rigorous justification of a generalized version of the widely used SERS enhancement factor proportional to the fourth power of the field ($|E|^4$). We show, in addition, that this approach also applies to the calculation of Surface-Enhanced Fluorescence cross-sections thus presenting both phenomena SERS and SEF within a unified framework.

physics.chem-ph↗

arXiv2005

Plasmon-mediated Polarization Anomalies in Surface Enhanced Raman Scattering (SERS)

We discuss the effect of the local field polarization in metallic nanostructures where large field enhancements can be induced by excitation of localized surface plasmons. To demonstrate the importance of these effects, we study a few model systems in 2D and 3D. As an experimental probe of this effect, we suggest to use depolarization ratios in Surface Enhanced Raman Spectroscopy (SERS) measurements. We attempt to relate the polarization of the local field to the depolarization ratios in SERS conditions. This approach could also lead to some better understanding of the SERS mechanisms at a microscopic level.

physics.chem-ph↗

arXiv2004

Quantum Mechanical Hysteresis and the Electron Transfer Problem

We study a simple quantum mechanical symmetric donor-acceptor model for electron transfer (ET) with coupling to internal deformations. The model contains several basic properties found in biological ET in enzymes and photosynthetic centers; it produces tunnelling with hysteresis thus providing a simple explanation for the slowness of the reversed rate and the near 100% efficiency of ET in many biological systems. The model also provides a conceptual framework for the development of molecular electronics memory elements based on electrostatic architectures.

quant-ph↗