TEMPERATURE-DEPENDENCE OF OPTICAL-ABSORPTION SPECTRA OF SOLVATED ELECTRONS IN CD3OD FOR T-LESS-THAN-OR-EQUAL-TO-T-C

Brodsky and Tsarevsky (J. Phys. Chem. 1984, 88, 3790) developed a theory on solvated electrons (e(solv)(-)) which is based on the concept that the excess electron is localized in a medium predominantly by short-range interactions. Including many-body collective effects of the solvent, they tried also to explain the temperature dependence of the optical absorption spectra of e(solv)(-). To substantiate their point of view, they presented experimental spectra of e(solv)(-) in CH3OH measured over a wide range of temperatures which were in ''satisfactory quantitative agreement'' with theory. We have carefully repeated optical absorption measurements on e(solv)(-) in CD3OD in the temperature range 298 less than or equal to T less than or equal to 510 K. We report on these experimental results and on the static dipole polarizability [alpha(0)] of solvated electrons in different media determined by means of optical sum rules. Both results are inconsistent with the above-mentioned theory. The comparison of other ground-state properties of solvated electrons in methanol such as the mean dispersion in position [Delta r(2)] and the mean quantum mechanical kinetic energy [T] following from the spectra with those obtained by a quantum molecular dynamics simulation shows poor agreement.