RT Journal Article
T1 A computational approach for electrochemical SERS.Key role of the surface charges and synergy between EM and CT mechanisms.
A1 Aranda, Daniel
A1 García-González, Francisco
A1 Ávila-Ferrer, Francisco José
A1 López-Tocón, Isabel
A1 Soto-Martín, Juan
A1 Otero-Fernández-de-Molina, Juan Carlos
K1 Espectroscopía Raman
AB We present a computational approach for electrochemical Surface-Enhanced Raman Scattering(EC-SERS). The surface excess of charge induced by the electrode potential (Vel) was introducedby applying an external electric  eld to a set of clusters [Agn]q with (n,q) of (19, 1) or (20,0) onwhich a molecule adsorbs. Using DFT/TD-DFT calculations, these metal-molecule complexes wereclassi ed by the adsorbate partial charge, and the main Vel-dependent properties were simultaneouslystudied with the aid of vibronic resonance Raman computations. Namely, changes on the vibrationalwavenumbers, relative intensities and enhancement factors for all SERS mechanisms: chemical ornonresonant, and resonance Raman with bright states of the adsorbate, charge-transfer states andplasmon-like excitations on the metal cluster. We selected two molecules to test our model, pyridine,for which Vel has a remarkable e ect, and 9,10-bis((E)-2-(pyridin-4-yl)vinyl)anthracene, which is almostinsensitive to the applied bias. The results nicely reproduced most of the experimental observations,while the limitations of our approach were critically evaluated. We detected that accounting explicitlyfor the surface charges is key for EC-SERS models and that the highest calculated enhancement factors,up to 107-108, are obtained by interstate coupling of bright local excitations of the metal cluster and
YR 2022
FD 2022-10-12
LK https://hdl.handle.net/10630/28327
UL https://hdl.handle.net/10630/28327
LA eng
NO J. Chem. Theory Comput. 2022, 18, 11, 6802–6815
NO University of Málaga and Generalitat Valenciana/European Social Fund(APOSTD/2021/025)University of Málaga for fundings (Predoctoralcontract A2 I Plan Propio de Investigación, Transferencia y Divulgación Científica).
DS RIUMA. Repositorio Institucional de la Universidad de Málaga
RD 3 mar 2026