Intermolecular Coulombic decay (ICD) is a well-established mechanism for energy transfer between core-excited atoms and their neighbors. In developing a theoretical explanation for ICD-related features in the x-ray photoelectron spectrum of NaOH(aq) [C. P. Schwartz, S. Fatehi, R. J. Saykally, and D. Prendergast, Phys. Rev. Lett. 105 , 198102 (2010)], some of the present authors proposed simple spatial and energetic criteria for the prediction of ICD targets. We refine these qualitative measures � in particular, we develop a nominal measure of excess overlap between chemically distinct contributions to the total density of states � and apply them to predict the preferred target for ICD from core-excited bismuth(III) in an aqueous solution containing citrate anions and 1,4-dioxane. Synchrotron experiments demonstrate not only that citrate is the target, as predicted, but that there is a fivefold enhancement in the citrate:dioxane destruction ratio over background radiolysis (i.e., in the absence of bismuth). We conclude with a brief discussion of how these insights may be developed further for use in cancer radiotherapy.

Qualitative criteria correctly predict targeted energy transfer in solution

246th National Meeting (2013)

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