Chemical effects on nuclear decay of $^{235}$U isomer in the uranyl form

Abstract

The nucleus of uranium-235 ($^{235}$U) possesses an exceptionally low-energy isomeric state, $^{235m}$U. Unlike most radioactive nuclides, whose nuclear-decay half-lives are constant, the half-life of $^{235m}$U varies with its chemical environment$^{1,2}$ owing to interactions with outer-shell electrons in the internal-conversion (IC) process. However, the mechanism underlying this half-life variation, particularly the role of molecular bonding beyond simple electron-density effects$^{1,2}$, remains unresolved. Here, we investigate variations in the half-lives of $^{235m}$U and the corresponding IC-electron energy spectra for uranyl (UO2$^{2+}$) compounds with different halide ligands. The half-lives of $^{235m}$U are measured to be 25.32(4), 26.05(8), 25.84(3), and 25.44(3) min for uranyl fluoride, chloride, bromide, and iodide, respectively, indicating that the half-life increases with increasing ligand electronegativity, with the exception of uranyl fluoride. The shortest half-life observed for uranyl fluoride is attributed to the smallest number of 6p electrons occupying bonding orbitals, as indicated by the IC-electron energy spectra and quantum chemical calculations. This work provides the first observation of a significant variation in a nuclear decay process driven by changes in molecular orbital formation, paving the way toward a deeper understanding of interactions between a nucleus and electrons involved in chemical bonding.