Ab Initio Investigation of Cooperativity in Ion Exchange

Daniel Dumett Torres, Prashant K. Jain

Research output: Contribution to journalArticlepeer-review


Ion exchange reactions are being increasingly employed for the templated synthesis of inorganic nanomaterials for plasmonics, topological quantum computing, and solid-state electrolytes. Some cation exchange reactions have been found to be cooperative akin to the nature of ligand binding processes in enzymes. What is the structural origin of this cooperative behavior? This question is answered here through computational simulations of Cd2+-to-Cu+ replacement reactions in a CdSe crystal. Density functional theory simulations show that the incorporation of Cu+, at the initial stages of exchange, induces a translocation of Cd2+ ions from their ideal tetrahedral sites to the otherwise unfavored octahedral sites. This reorganized structure has a lower energy cost for Cd2+-to-Cu+ replacement and is therefore much more amenable to further cation exchange. Thus, Cu+-insertion-induced reorganization of the cationic sublattice is at the origin of the cooperativity exhibited by the cation exchange reaction. This atomic-level understanding establishes a close link between solid-state chemical reactions and phase transitions and will lead to more precise transformations for accessing unusual material phases.

Original languageEnglish (US)
Pages (from-to)25615-25620
Number of pages6
JournalJournal of Physical Chemistry C
Issue number46
StatePublished - Nov 19 2020

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films


Dive into the research topics of 'Ab Initio Investigation of Cooperativity in Ion Exchange'. Together they form a unique fingerprint.

Cite this