Hydrogen-induced suppression of the optical plasmonic response in ultra-small gold nanoparticles
Abstract
In this study, we investigate how hydrogen adsorption modifies the structure, electronic properties, and optical response of sub-3 nm gold nanoparticles (NPs) using DFT for structural relaxations and real-time TDDFT(+U) for the absorption spectra. Under vacuum, a full monolayer of adsorbed hydrogen drives pronounced surface restructuring into Au-H-Au-H chain motifs and induces a net electron transfer from Au to adsorbed H, stabilizing the hydrogenated shell. These changes shift and broaden the electronic density of states and strongly affect plasmonic features. Thus, while bare Au NPs display the localized surface-plasmon resonance (LSPR) for diameters larger than 2 nm, hydrogenation markedly diminishes the resonance, nearly quenching it for particles below 3 nm. Comparison with constrained geometries indicates that Au-H bonding and charge transfer primarily drive LSPR suppression, whereas structural distortion mainly contributes to spectral broadening. Our results suggest that hydrogen adsorption can profoundly change the plasmonic signature of ultrasmall Au NPs, providing important insight into the interpretation of their optical spectra under hydrogen-rich conditions.
Computational details
Structural relaxationTo perform the structural optimizations and electronic structure analysis, we employed density-functional theory (DFT) as implemented in the Vienna ab initio simulation package (VASP). 9,10
Related
- Deciphering Aggregation-Induced Tunable Circular Dichroism of AuBP@Ag and AuBP@Au Chiral Core–Shell Plasmonic Nanoparticles
- Thermally switchable plasmonic optical response of Au@PEtOx-stat-PBuOx core-shell nanoparticles with a tunable switching point
- Hydrogen-Bond-Induced Dual Structural Response in Amide-Functionalized Self-Assembled Monolayers
- Probing the dimensionality of confinement in soft nanoreactors through plasmonic nanoparticles nucleation
- Plasmonic behaviour of poly(2-ethyl-2-oxazoline)-coated gold nanoparticles for sensing and temperature-control applications
BibTeX
@article{chaudhary2026hydrogeninduced,
title = {{Hydrogen-induced suppression of the optical plasmonic response in ultra-small gold nanoparticles}},
author = {Mohit Chaudhary and Loréna Chabeaud and Ranjan Bassi and Hazar Guesmi and Hans-Christian Weissker},
journal = {Physical Chemistry Chemical Physics},
year = {2026},
month = aug,
doi = {10.1039/d6cp00557h},
url = {https://hal.science/hal-05790362v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Hydrogen-induced suppression of the optical plasmonic response in ultra-small gold nanoparticles
AU - Mohit Chaudhary
AU - Loréna Chabeaud
AU - Ranjan Bassi
AU - Hazar Guesmi
AU - Hans-Christian Weissker
PY - 2026
DA - 2026/08/25
JO - Physical Chemistry Chemical Physics
DO - 10.1039/d6cp00557h
UR - https://hal.science/hal-05790362v1
AB - In this study, we investigate how hydrogen adsorption modifies the structure, electronic properties, and optical response of sub-3 nm gold nanoparticles (NPs) using DFT for structural relaxations and real-time TDDFT(+U) for the absorption spectra. Under vacuum, a full monolayer of adsorbed hydrogen drives pronounced surface restructuring into Au-H-Au-H chain motifs and induces a net electron transfer from Au to adsorbed H, stabilizing the hydrogenated shell. These changes shift and broaden the electronic density of states and strongly affect plasmonic features. Thus, while bare Au NPs display the localized surface-plasmon resonance (LSPR) for diameters larger than 2 nm, hydrogenation markedly diminishes the resonance, nearly quenching it for particles below 3 nm. Comparison with constrained geometries indicates that Au-H bonding and charge transfer primarily drive LSPR suppression, whereas structural distortion mainly contributes to spectral broadening. Our results suggest that hydrogen adsorption can profoundly change the plasmonic signature of ultrasmall Au NPs, providing important insight into the interpretation of their optical spectra under hydrogen-rich conditions. Computational details Structural relaxationTo perform the structural optimizations and electronic structure analysis, we employed density-functional theory (DFT) as implemented in the Vienna ab initio simulation package (VASP). 9,10
SN - 1463-9076
SN - 1463-9084
ER -