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 theo ry on solvated electrons (e(solv)(-)) which is based on the concept th at the excess electron is localized in a medium predominantly by short -range interactions. Including many-body collective effects of the sol vent, they tried also to explain the temperature dependence of the opt ical absorption spectra of e(solv)(-). To substantiate their point of view, they presented experimental spectra of e(solv)(-) in CH3OH measu red over a wide range of temperatures which were in ''satisfactory qua ntitative agreement'' with theory. We have carefully repeated optical absorption measurements on e(solv)(-) in CD3OD in the temperature rang e 298 less than or equal to T less than or equal to 510 K. We report o n 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-me ntioned theory. The comparison of other ground-state properties of sol vated electrons in methanol such as the mean dispersion in position [D elta r(2)] and the mean quantum mechanical kinetic energy [T] followin g from the spectra with those obtained by a quantum molecular dynamics simulation shows poor agreement.