title: Spatial resolution of tip-enhanced Raman spectroscopy - DFT assessment of the chemical effect.
abstract: Experimental evidence of extremely high spatial resolution of tip-enhanced Raman scattering (TERS) has been recently demonstrated. Here, we present a full quantum chemical description (at the density functional level of theory) of the non-resonant chemical effects on the Raman spectrum of an adenine molecule mapped by a tip, modeled as a single silver atom or a small silver cluster. We show pronounced changes in the Raman pattern and its intensities depending on the conformation of the nanoparticle-substrate system, concluding that the spatial resolution of the chemical contribution of TERS can be in the sub-nm range.
authors.affiliation: Institute of Physical Chemistry and Abbe Center of Photonics, Friedrich-Schiller-University Jena, Helmholtzweg 4, 07743 Jena, Germany. stephan.kupfer@uni-jena.de volker.deckert@uni-jena.de.
authors.forename: Federico
authors.initials: F
authors.lastname: Latorre
authors.forename: Stephan
authors.initials: S
authors.lastname: Kupfer
authors.forename: Thomas
authors.initials: T
authors.lastname: Bocklitz
authors.forename: Daniel
authors.initials: D
authors.lastname: Kinzel
authors.forename: Steffen
authors.initials: S
authors.lastname: Trautmann
authors.forename: Stefanie
authors.initials: S
authors.lastname: Gräfe
authors.forename: Volker
authors.initials: V
authors.lastname: Deckert