On the insensitivity of the non-adiabatic relaxation of solvated electrons to the details of their local solvent environment

Utilizing the charge-transfer-to-solvent transition of Na−, we measure the excited-state lifetime of the solvated electron (es−) in tetrahydrofuran (THF) in each of three different well-defined local solvent environments: an isolated THF cavity, a THF cavity with a sodium atom located one solvent shell away, and a THF cavity with a sodium atom in the first solvent shell. We find that the excited-state lifetimes of the es− in each environment are the same, suggesting that the solvent-induced non-adiabatic coupling that determines the radiationless transition rate is insensitive to the details of the specific atoms or molecules in the first solvent shell.