# Field-Gated Anion Transport in Nanoparticle Superlattices Controlled by Charge Density and Ion Geometry: Insights from Molecular Dynamics Simulations

## TL;DR

This study uses simulations to explore how anion shape and charge affect ion transport in nanoparticle superlattices under electric fields.

## Contribution

The paper reveals that linear anions enhance conductivity more than ring-shaped ones due to higher charge density and weaker binding.

## Key findings

- Linear anions outperform ring-shaped anions in conductivity due to higher charge density and weaker interfacial binding.
- Strong electric fields cause anion accumulation at nanoparticle interfaces, suppressing transport due to adsorption and steric constraints.
- Cyclic anions face mobility barriers due to their rigidity and delocalized charge, as shown by transition probability and residence time analyses.

## Abstract

Nanoparticle superlattices—periodic assemblies of uniformly spaced nanocrystals—bridge the nanoscale precision of individual particles with emergent collective properties akin to those of bulk materials. Recent advances demonstrate that multivalent ions and charged polymers can guide the co-assembly of nanoparticles, imparting electrostatic gating and enabling semiconductor-like behavior. However, the specific roles of anion geometry, valency, and charge density in mediating ion transport remain unclear. Here, we employ coarse-grained molecular dynamics simulations to investigate how applied electric fields (0–0.40 V/nm) modulate ionic conductivity and spatial distribution in trimethylammonium-functionalized gold nanoparticle superlattices assembled with four phosphate anions of distinct geometries and charges. Our results reveal that linear anions outperform ring-shaped analogues in conductivity due to higher charge densities and weaker interfacial binding. Notably, charge density exerts a greater influence on ion mobility than size alone. Under strong fields, anions accumulate at nanoparticle interfaces, where interfacial adsorption and steric constraints suppress transport. In contrast, local migration is governed by geometrical confinement and field strength. Analyses of transition probability and residence time further indicate that the rigidity and delocalized charge of cyclic anions act as mobility barriers. These findings provide mechanistic insights into the structure–function relationship governing ion transport in superlattices, offering guidance for designing next-generation ion conductors, electrochemical sensors, and energy storage materials through anion engineering.