Effect of alkylation of ammonia on the optical band shape of solvated electrons

At 200 K the width at half height, W1/2, of the e−solv optical absorption band in n-propyl amine is 2.1-fold greater than that in ammonia. Three quarters of the broadening occurs on the high energy side of the band. The energy Er at half height on the low energy side of the band is nearly the same in the amine as in ammonia, while Eb, the energy at half height on the high energy side, is 42% greater in the amine. The temperature coefficient dEAmax/dT is 1.8-fold greater in the amine than in ammonia. The larger width is consistent with there being a less uniform distribution of localization sites in the system, and the larger temperature coefficient implies that the sites are more easily disturbed by thermal agitation. A quantum statistical mechanical model, such as the one begun by Simons, is needed to extend the theoretical treatment of e−solv spectra. The correlation between optical absorption energies of e−solv and the structure of the solvent, as partially reflected in the Kirkwood correlation factor, is re-emphasized.