Electronic Bound States of Solvated Electrons in High Chemical Hardness Solvents

Solvated electrons are highly reactive species that can drive many high-energy redox reactions. This study presents an efficient computational method to calculate the electronic bound states of the solvated electron. In chemically hard solvents, the interaction with the solvated electron can be captured by a constrained self-consistent field optimization of solvent polarization, followed by a single-step GW correction for exchange–correlation effects. Using water and ammonia as examples, the energies of these bound states agree with benchmark CCSD(T) electron affinities within 7%, and their wave functions reproduce the spatial distribution of the solvated electron. Furthermore, this method scales as O(n³), which enables large-scale simulations of solvated electron dynamics.