A Joint Photoelectron Spectroscopy and Theoretical Study on the Electronic Structure of UCl5− and UCl5. Issue 10 (12th July 2013)

• Record Type: Journal Article
• Authors: Su, Jing; Dau, Phuong Diem; Xu, Chao‐Fei; Huang, Dao‐Ling; Liu, Hong‐Tao; Wei, Fan; Wang, Lai‐Sheng; Li, Jun
• Is Part Of: Chemistry, an Asian journal. Volume 8:Issue 10(2013:Oct.)
• Page Start: 2489
• Page End: 2496
• Publication Date: 2013-07-12
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.201300627
• Languages: English
• ISSNs: 1861-4728

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>We report a combined photoelectron spectroscopic and relativistic quantum chemistry study on gaseous UCl<sub>5</sub><sup>−</sup> and UCl<sub>5</sub>. The UCl<sub>5</sub><sup>−</sup> anion is produced using electrospray ionization and found to be highly electronically stable with an adiabatic electron binding energy of 4.76±0.03 eV, which also represents the electron affinity of the neutral UCl<sub>5</sub> molecule. Theoretical investigations reveal that the ground state of UCl<sub>5</sub><sup>−</sup> has an open shell with two unpaired electrons occupying two primarily U 5f<mml:math overflow="scroll" xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:msub><mml:mtext> </mml:mtext><mml:mrow><mml:mtext fontstyle="italic">z</mml:mtext><mml:msup><mml:mtext> </mml:mtext><mml:mrow><mml:mtext>3</mml:mtext></mml:mrow></mml:msup></mml:mrow></mml:msub></mml:math><inline-graphic xlink:href="ark:/27927/pgg3hbk5n0q" mimetype="image" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /> and 5f<sub><italic>xyz</italic></sub> based molecular orbitals. The structures of both UCl<sub>5</sub><sup>−</sup> and UCl<sub>5</sub> are theoretically optimized and confirmed to have <italic>C</italic><sub>4<italic>v</italic></sub> symmetry. The computational results are in good agreement with the photoelectron spectra, providing insights into the electronic structures and valence molecular orbitals of UCl<sub>5</sub><sup>−</sup> and UCl<sub>5.</sub> We also performed systematic theoretical studies on all the uranium pentahalide complexes UX<sub>5</sub><sup>−</sup> (X=F, Cl, Br, I). Chemical bonding analyses indicate that the UX interactions in UX<sub>5</sub><sup>−</sup> are dominated by ionic bonding, with increasing covalent contributions for the heavier halogen complexes.</p> </abstract>