Theoretical basis for the stabilization of charges by radicals on electrified polymers

Abstract

Quantum mechanical calculations at various levels of theory indicate that charges (both "+" and "-") on organic polymers can be stabilized by radicals on nearby polymer chains. The stabilization mechanism is based on the formation of intermolecular odd-electron, two-center bonds with possible concomitant spin density redistribution (depending on the polymer and the number and type of proximal heteroatoms). This result is in line with our previous experimental demonstrations that on various types of polymers charged by contact electrification, radicals co-localize and help stabilize proximal charges (of either polarity). The principle of intramolecular charge-radical stabilization we now confirm on a fundamental level might have ramifications for the design of other macromolecular systems in which chemical reactivity is controlled by radicals flanking the charged groups or by charged groups flanking the radicals.