Zhang Cui, Hu Shu-Xian, Liu Hai-Tao, Yang Yu, Zhang Ping
Institute of Applied Physics and Computational Mathematics, P.O. Box 8009, Beijing 100088 , People's Republic of China.
Beijing Computational Science Research Center, Beijing 100193 , People's Republic of China.
J Phys Chem A. 2018 Apr 26;122(16):4085-4091. doi: 10.1021/acs.jpca.7b12324. Epub 2018 Apr 16.
The structural and electronic properties of PuO ( 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 PuO and PuO 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.
在筛选后的杂化密度泛函理论框架内，对PuOₙ（n = 1 - 8）分子的结构和电子性质进行了系统研究。基于计算结果，钚和氧通常更倾向于形成Pu - O键和Pu - O - Pu键，而非Pu - Pu键或O - O键。在基态几何结构中，我们发现钚原子的最高氧化态为Pu(VI)。通过碎片研究，我们发现在所有研究的化合物中，PuO和PuO₂分子在能量上是稳定的。当将费米能级固定为能量零点时，Pu - 5f态总是分布在费米能级两侧。随着氧原子数量和钚氧化态的增加，Pu - 6d态从费米能级上方下移至下方。
