Interaction of boron cluster ions with water: Single collision dynamics and sequential etching

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Abstract
Reactions of mass‐selected, cooled, boron cluster ions (B+n, n=1–14) with water have been studied for collision energies from 0.1 to 6.0 eV. Most work was done with D2O, however isotope effects were examined for selected reactant cluster ions. For all size clusters there are exoergic product channels, which in most cases have no activation barriers. Cross sections are generally large, however there are fluctuations with cluster size in total reactivity, collision energy dependences, and in product distributions. For small cluster ions, there is a multitude of product channels. For clusters larger than B+6, the product distributions are dominated by a single channel: Bn−1D++DBO. Under multiple collision conditions, the primary products undergo a remarkable sequence of secondary ‘‘etching’’ reactions. As these occur, boron atoms are continuously replaced by hydrogen, and the intermediate products retain the composition: Bn−mH+m. This highly efficient chemistry appears to continue unchanged as the composition changes from pure boron to mostly hydrogen. Comparison of these results is made with boron cluster ion reactions with O2 and D2, as well as reactions with water of aluminum and silicon cluster ions. Some discussion is given of the thermochemistry for these reactions, and a possible problem with the thermochemical data in the BOD/DBO system is discussed.

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