TY  - JOUR
A1  - Stefancu, Andrei
A1  - Nan, Lin
A1  - Zhu, Li
A1  - Chis, Vasile
A1  - Bald, Ilko
A1  - Liu, Min
A1  - Leopold, Nicolae
A1  - Maier, Stefan A.
A1  - Cortes, Emiliano
T1  - Controlling plasmonic chemistry pathways through specific ion effects
JF  - Advanced optical materials
N2  - Plasmon-driven dehalogenation of brominated purines has been recently explored as a model system to understand fundamental aspects of plasmon-assisted chemical reactions. Here, it is shown that divalent Ca2+ ions strongly bridge the adsorption of bromoadenine (Br-Ade) to Ag surfaces. 
Such ion-mediated binding increases the molecule's adsorption energy leading to an overlap of the metal energy states and the molecular states, enabling the chemical interface damping (CID) of the plasmon modes of the Ag nanostructures (i.e., direct electron transfer from the metal to Br-Ade). 
Consequently, the conversion of Br-Ade to adenine almost doubles following the addition of Ca2+. 
These experimental results, supported by theoretical calculations of the local density of states of the Ag/Br-Ade complex, indicate a change of the charge transfer pathway driving the dehalogenation reaction, from Landau damping (in the lack of Ca2+ ions) to CID (after the addition of Ca2+). 
The results show that the surface dynamics of chemical species (including water molecules) play an essential role in charge transfer at plasmonic interfaces and cannot be ignored. It is envisioned that these results will help in designing more efficient nanoreactors, harnessing the full potential of plasmon-assisted chemistry.
KW  - chemical interface damping
KW  - Hofmeister effect
KW  - hydration layer
KW  - plasmonic chemistry
KW  - specific ion effects
KW  - surface-enhanced Raman scattering
Y1  - 2022
U6  - https://doi.org/10.1002/adom.202200397
SN  - 2195-1071
VL  - 10
IS  - 14
PB  - Wiley-VCH
CY  - Weinheim
ER  -