Single-molecule vibrational pumping in SERS

Literature Information

Publication Date 2009-06-29
DOI 10.1039/B904638K
Impact Factor 3.676
Authors

C. M. Galloway, E. C. Le Ru, P. G. Etchegoin


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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.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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