By reacting laser-ablated uranium atoms in the presence of nitrogen, new spectroscopic peaks, in particular products containing more than one uranium center, have been characterized by means of infrared spectroscopy and theoretical studies. Through the combined use of hybrid density functional theory (DFT), complete active space SCF theory with corrections from second-order perturbation theory (CASSCF/CASPT2) calculations, and restricted active space SCF theory with corrections from second-order perturbation theory (RASSCF/RASPT2) new peaks in the infrared region have been identified including a cyclic (UN)2 molecule with unconventional bonding. While this novel species does not have a direct U-U bond, three-centered bonds between the U 5f and 6d orbitals and the nitrogen 2p orbitals provide substantial stabilization to thermodynamically drive the formation of this unique product. The linear isomer as well as a thorium analogue will also be discussed.

Electronic structure of uranium and nitrogen molecules with multiple uranium atoms

248th National Meeting (2014)

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