Quantifying solvated electrons' delocalization

Janesko, Benjamin G.; Scalmani, Giovanni; Frisch, Michael J.

Publication

Quantifying solvated electrons' delocalization

Janesko, Benjamin G.; Scalmani, Giovanni; Frisch, Michael J.

Publisher

The Royal Society of Chemistry

Date

2015-05-21

Abstract

Delocalized, solvated electrons are a topic of much recent interest. We apply the electron delocalization range EDR([r (vector)];u) (J. Chem. Phys., 2014, 141, 144104) to quantify the extent to which a solvated electron at point [r with combining right harpoon above [r (vector)] 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.