Ultrafast vibrational dynamics of BH4(-) ions in liquid and crystalline environments.

Abstract

Ultrafast vibrational dynamics of BH4(-) ions, the key units in boron hydride materials for hydrogen storage, are studied in diluted polar liquid solution and in NaBH4 crystallites by femtosecond infrared spectroscopy. Two-color pump-probe experiments reveal v = 1 lifetimes of 3 ps for the asymmetric BH4(-) stretching mode ν3 and of 3.6 ps for the asymmetric bending mode ν4 in the solvent isopropylamine. We provide direct evidence for the BH4(-) stretching relaxation pathway via the asymmetric bending mode ν4 by probing the latter after femtosecond excitation of ν3. Pump-probe traces measured in the crystalline phase show signatures of radiative coupling between the densely packed BH4(-) oscillators, most clearly manifested in an accelerated subpicosecond depopulation of the v = 1 state of the ν4 mode. The radiative decay is followed by incoherent vibrational relaxation similar to the liquid phase. The excess energy released in the relaxation processes of the BH4(-) intramolecular modes is transferred into the environment with thermal pump-probe signals being much more pronounced in the dense solid than in the diluted solution.