American Chemical Society
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Dynamics of Dihydrogen Bonding in Aqueous Solutions of Sodium Borohydride

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journal contribution
posted on 2015-02-26, 00:00 authored by Chiara H. Giammanco, Patrick L. Kramer, Michael D. Fayer
Dihydrogen bonding occurs between protonic and hydridic hydrogens which are bound to the corresponding electron withdrawing or donating groups. This type of interaction can lead to novel reactivity and dynamic behavior. This paper examines the dynamics experienced by both borohydride and its dihydrogen-bound water solvent using 2D-IR vibrational echo and IR pump–probe spectroscopies, as well as FT-IR linear absorption experiments. Experiments are conducted on the triply degenerate B–H stretching mode and the O–D stretch of dilute HOD in the water solvent. While the B–H stretch absorption is well separated from the broad absorption band of the OD of HOD in the bulk of the water solution, the absorption of the ODs hydrogen bonded to BHs overlaps substantially with the absorption of ODs in the bulk H2O solution. A subtraction technique is used to separate out the anion-associated OD dynamics from that of the bulk solution. It is found that both the water and borohydride undergo similar spectral diffusion dynamics, and these are very similar to those of HOD in bulk water. Because the B–H stretch is triply degenerate, the IR pump–probe anisotropy decays very rapidly, but the decay is not caused by the physical reorientation of the BH4 anions. Spectral diffusion occurs on a time scale longer than the anisotropy decay, demonstrating that spectral diffusion is not yet complete even when the transition dipole has completely randomized. To prevent chemical decomposition of the BH4, 1 M NaOH was added to stabilize the system. 2D-IR experiments on the OD stretch of HOD in the NaOH/water liquid (no borohydride) show that the NaOH has a negligible effect on the bulk water dynamics.