title: Quantifying solvated electrons' delocalization.
abstract: Delocalized, solvated electrons are a topic of much recent interest. We apply the electron delocalization range EDR(r;u) (J. Chem. Phys., 2014, 141, 144104) to quantify the extent to which a solvated electron at point r in a calculated wavefunction delocalizes over distance u. Calculations on electrons in one-dimensional model cavities illustrate fundamental properties of the EDR. Mean-field calculations on hydrated electrons (H2O)n(-) show that the density-matrix-based EDR reproduces existing molecular-orbital-based measures of delocalization. Correlated calculations on hydrated electrons and electrons in lithium-ammonia clusters illustrates how electron correlation tends to move surface- and cavity-bound electrons onto the cluster or cavity surface. Applications to multiple solvated electrons in lithium-ammonia clusters provide a novel perspective on the interplay of delocalization and strong correlation central to lithium-ammonia solutions' concentration-dependent insulator-to-metal transition. The results motivate continued application of the EDR to simulations of delocalized electrons.
authors.affiliation: Texas Christian University, Fort Worth, TX 76129, USA. b.janesko@tcu.edu.
authors.forename: Benjamin G
authors.initials: BG
authors.lastname: Janesko
authors.forename: Giovanni
authors.initials: G
authors.lastname: Scalmani
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Frisch