Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 7, Issue 4, Pages 627-631Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.5b02547
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Funding
- Department of Education through Graduate Assistance in Areas of National Need Fellowship
- U.S. National Science Foundation [CHE-1152425]
- U.S. Army Research Office (ARO) STTR [W911NF-16-C-0030]
- U.S. Air Force Office of Scientific Research (AFOSR) [FA9550-14-1-0367]
- W. M. Keck Foundation
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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.
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