Print Email Facebook Twitter Atomistic understanding of cation exchange in PbS nanocrystals using simulations with pseudoligands Title Atomistic understanding of cation exchange in PbS nanocrystals using simulations with pseudoligands Author Fan, Z. (TU Delft Engineering Thermodynamics) Lin, L. (TU Delft Engineering Thermodynamics) Buijs, W. (TU Delft Engineering Thermodynamics) Vlugt, T.J.H. (TU Delft Engineering Thermodynamics) van Huis, MA Date 2016 Abstract Cation exchange is a powerful tool for the synthesis of nanostructures such as core–shell nanocrystals, however, the underlying mechanism is poorly understood. Interactions of cations with ligands and solvent molecules are systematically ignored in simulations. Here, we introduce the concept of pseudoligands to incorporate cation-ligand-solvent interactions in molecular dynamics. This leads to excellent agreement with experimental data on cationexchange of PbS nanocrystals, whereby Pb ions are partially replaced by Cd ions from solution. The temperature and the ligand-type control the exchange rate and equilibrium composition of cations in the nanocrystal. Our simulations reveal that Pb ions are kicked out by exchanged Cd interstitials and migrate through interstitial sites, aided by local relaxations at core–shell interfaces and point defects. We also predict that high-pressure conditions facilitate strongly enhanced cation exchange reactions at elevated temperatures. Our approach is easily extendable to other semiconductor compounds and to other families ofnanocrystals. Subject chemical sciencesphysical chemistrynanotechnology To reference this document use: http://resolver.tudelft.nl/uuid:de954ea2-905b-4e24-8040-e60088af6eba DOI https://doi.org/10.1038/ncomms11503 ISSN 2041-1723 Source Nature Communications, 7, 1-8 Part of collection Institutional Repository Document type journal article Rights © 2016 Z. Fan, L. Lin, W. Buijs, T.J.H. Vlugt, MA van Huis Files PDF ncomms11503.pdf 1.94 MB Close viewer /islandora/object/uuid:de954ea2-905b-4e24-8040-e60088af6eba/datastream/OBJ/view