Bonding Properties and Oxidation States of Plutonium in Pu2O n ( n = 1-8) Molecules Studied by Using Screened Hybrid Density Functional Theory

Cui Zhang; Shu-Xian Hu; Hai-Tao Liu; Yu Yang; Ping Zhang

doi:10.1021/acs.jpca.7b12324

Bonding Properties and Oxidation States of Plutonium in Pu₂O _n ( n = 1-8) Molecules Studied by Using Screened Hybrid Density Functional Theory

J Phys Chem A. 2018 Apr 26;122(16):4085-4091. doi: 10.1021/acs.jpca.7b12324. Epub 2018 Apr 16.

Authors

Cui Zhang¹, Shu-Xian Hu², Hai-Tao Liu¹, Yu Yang¹, Ping Zhang¹

Affiliations

¹ Institute of Applied Physics and Computational Mathematics, P.O. Box 8009, Beijing 100088 , People's Republic of China.
² Beijing Computational Science Research Center, Beijing 100193 , People's Republic of China.

PMID: 29641202
DOI: 10.1021/acs.jpca.7b12324

Abstract

The structural and electronic properties of Pu₂O _n ( n = 1-8) molecules have been systematically studied within the screened hybrid density functional theory. On the basis of the calculations, plutonium and oxygen generally prefers forming Pu-O and Pu-O-Pu bonds over to Pu-Pu or O-O bonds. In the ground-state geometries, we find that the highest oxidation state for plutonium atoms is Pu(VI). Through fragmentation studies, we find that the Pu₂O and Pu₂O₂ molecules are energetically stable among all studied compounds. When fixing the Fermi level to be energy zero, the Pu-5 f states always distribute at the two sides of the Fermi level. With increasing the number of oxygen atoms and the oxidation state of plutonium, the Pu-6d states shift down from above to below the Fermi level.