On the Physical Nature of Uranyl Charge Transfer Vibronic Interactions

Abstract

ABSTRACTWe address the electronic properties of uranyl ions in solids and solutions with an emphasis in theoretical understanding of charge transfer vibronic transitions and luminescence dynamics the O-U-O species. A general theory of ion-phonon interaction has been modified for modeling and simulating multi-phonon vibronic spectra. Spectroscopic data for uranyl ions in crystals and solutions have been analyzed to achieve a predictive understanding of the uranyl-ligand vibronic interactions. By adjusting the Huang-Rhys ion-phonon interaction parameters, an excellent agreement between theory and experiment has been accomplished for uranyl ions in the ligand environments we studied. Our modeling and simulation provide insights into the physical nature of uranyl vibronic interaction and its influence on spectroscopic properties, which are commonly utilized in characterizing photochemical properties of uranyl in complexes.