Speaker
Description
We present the first observation of vibrational transitions in the [H3O]− anion, an intermediate in the anion–molecule reaction of water, H2O, and hydride, H–, using a laser-induced isotopic H/D exchange reaction action spectroscopy scheme applied to anions. The observed bands are assigned as the fundamental and first overtone of the H2O–H– vibrational stretching mode, based on anharmonic calculations within the vibrational perturbation theory and vibrational configuration interaction. Although the D2O·D– species has the lowest energy, our experiments confirm the D2O·H– isotope to be a sink of the H/D exchange reaction. Ab initio calculations corroborate that the formation of D2O·H– is favored, as the zero-point-energy difference is larger between D2 and H2 than between D2O·H– and D2O·D–.
J. Am. Chem. Soc. 2024, 146, 31, 21634–21641
