title: Entangled Electrons Foil Synthesis of Elusive Low-Valent Vanadium Oxo Complex.
abstract: We examine the recently reported first synthesis of the elusive low-valent vanadium(III) in a vanadium oxo complex with a computation representing 10(21) quantum degrees of freedom. While this computation is intractable with a conventionally constructed wave function, it is performed here by a direct calculation of the system's two-electron reduced density matrix (2-RDM), where the 2-RDM is constrained by nontrivial conditions, known as N-representability conditions, that restrict the 2-RDM to represent an N electron quantum system. We show that the added (reducing) electron becomes entangled among the five pyridine ligands. While smaller calculations predict a metal-centered addition, large-scale 2-RDM calculations show that quantum entanglement redirects the electron transfer to the pyridine ligands, resulting in a ligand-centered addition. Beyond its implications for the synthesis of low-valent vanadium oxo complexes, the result suggests new possibilities for using quantum entanglement to predict and control electron transfer in chemical and biological materials.
authors.affiliation: The Department of Chemistry and The James Franck Institute, The University of Chicago , Chicago, Illinois 60637, United States.
authors.forename: Anthony W
authors.initials: AW
authors.lastname: Schlimgen
authors.affiliation: The Department of Chemistry and The James Franck Institute, The University of Chicago , Chicago, Illinois 60637, United States.
authors.forename: Charles W
authors.initials: CW
authors.lastname: Heaps
authors.affiliation: The Department of Chemistry and The James Franck Institute, The University of Chicago , Chicago, Illinois 60637, United States.
authors.forename: David A
authors.initials: DA
authors.lastname: Mazziotti