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Tracking and Controlling Monolayer Water in Gold Nanogaps using Extreme Plasmonic Spectroscopy.

Elle W Wyatt¹, Sarah May Sibug-Torres¹, Rakesh Arul¹

¹NanoPhotonics Centre, Cavendish Laboratory, Department of Physics, University of Cambridge, JJ Thompson Avenue, Cambridge, CB3 0US, UK.

Small (Weinheim an Der Bergstrasse, Germany)

|October 25, 2025

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This summary is machine-generated.

Investigating water in nanogaps using surface-enhanced Raman spectroscopy (SERS) reveals persistent water monolayers on ostensibly dry surfaces. Applied potentials alter water orientation, offering insights into molecular interactions within confined spaces.

Area of Science:

Physical Chemistry
Materials Science
Nanotechnology

Background:

Nanogaps confine molecules, altering chemical reactions relevant to catalysis, corrosion, photochemistry, and sensing.
Understanding water structure in nanogaps under ambient conditions is crucial but challenging.

Purpose of the Study:

To investigate the solvation and structure of water within sub-nanometer gaps at coinage metal nanoparticle surfaces.
To determine the presence and behavior of water on nominally dry nanogap surfaces.

Main Methods:

Utilized multi-layer aggregates of gold nanoparticles with precisely defined sub-nanometer gaps.
Employed surface-enhanced Raman spectroscopy (SERS) to study water structure and interactions.
Applied negative potentials and used deuterated water for comparative analysis.

Keywords:

AuNP aggregates SERS nanogap sensing water

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Main Results:

Identified water monolayer coatings on nanogap surfaces exposed to air, even when nominally dry.
Observed re-orientation of surface water under applied negative potentials, with spectral shifts indicating water dimer interactions.
Characterized the binding of individual water molecules to organic spacer molecules within the nanogaps.

Conclusions:

Water molecules persist on nanogap surfaces even in ambient air, forming monolayer coatings.
Applied potentials significantly influence water structure and orientation at the metal-nanoparticle interface.
Detailed understanding of water-nanomaterial interactions is essential for advancing catalysis and contact chemistry.