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Electrochemical TERS Elucidates Potential‐Induced Molecular Reorientation of Adenine/Au(111)
Author(s) -
Martín Sabanés Natalia,
Ohto Tatsuhiko,
Andrienko Denis,
Nagata Yuki,
Domke Katrin F.
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201704460
Subject(s) - electrochemistry , protonation , molecule , raman spectroscopy , chemistry , chemical physics , deprotonation , adsorption , reactivity (psychology) , electrode potential , electrode , electrochemical potential , cyclic voltammetry , planar , computational chemistry , materials science , nanotechnology , organic chemistry , physics , optics , medicine , ion , alternative medicine , computer graphics (images) , pathology , computer science
Abstract Electrochemical surface activity arises from the interaction and geometric arrangement of molecules at electrified interfaces. We present a novel electrochemical tip‐enhanced Raman spectroscope that can access the vibrational fingerprint of less than 100 small, non‐resonant molecules adsorbed at atomically flat Au electrodes to study their adsorption geometry and chemical reactivity as a function of the applied potential. Combining experimental and simulation data for adenine/Au(111), we conclude that protonated physisorbed adenine adopts a tilted orientation at low potentials, whereas it is vertically adsorbed around the potential of zero charge. Further potential increase induces adenine deprotonation and reorientation to a planar configuration. The extension of EC‐TERS to the study of adsorbate reorientation significantly broadens the applicability of this advanced spectroelectrochemical tool for the nanoscale characterization of a full range of electrochemical interfaces.