Field-Gated Anion Transport in Nanoparticle Superlattices Controlled by Charge Density and Ion Geometry: Insights from Molecular Dynamics Simulations
Year: 2025
Type: article
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.
Source: Biomolecules
DOI: 10.3390/biom15101427
Institutions: Zhejiang University, Columbia University
Language: English
Subfield: Physical and Theoretical Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $3,258
Funders: Zhejiang University, Major Projects of Special Development Funds in Zhangjiang National Independent Innovation Demonstration Zone, Shanghai, Sichuan Province Science and Technology Support Program, National Key Research and Development Program of China, Shanghai Artificial Intelligence Laboratory
OpenAlex ID: W4414977542