A DFT Insight on LnPu+ (L = C4H4, C5H5, C6H6; n = 1–3) Complexes: Nature of Interactions and Electronic Spectroscopy. Issue 10 (9th March 2016)

• Record Type: Journal Article
• Authors: Du, Jiguang; Jiang, Gang
• Is Part Of: European journal of inorganic chemistry. Issue 10(2016)
• Page Start: 1589
• Page End: 1595
• Publication Date: 2016-03-09
• Subjects: Plutonium -- Actinides -- Density functional calculations -- Computer chemistry; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201501412
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The structures, bonding nature, and electronic spectra of Pu + –hydrocarbon complexes were investigated by using DFT. Our results indicate that electron promotion from 7s to 6d orbitals occurs when the Pu + ion is involved in chemical bonding. Nucleus‐independent chemical shift (NICS) values and electron localization function (ELF) analyses suggest that Pu + C5 H5 is aromatic and shows a large reinforcement of the ring delocalization. The weakly covalent characters of Pu + –C bonds were revealed by quantum theory of atoms in molecules (QTAIM) topological analyses. Simulated electronic spectra show that the absorption bands are localized at 200–500 nm and are mainly attributed to the Pu(f)→Pu(d) transition or LMCT. Abstract : The structures, bonding nature, and electronic spectra of simple L n Pu + (L = C4 H4, C5 H5, C6 H6 ; n = 1–3) complexes were investigated with DFT. The aromaticity of Pu + C5 H5 was studied by nucleus‐independent chemical shift (NICS) and electron localization function (ELF) analyses. The Pu + –C bonds are weakly covalent. The electronic spectra were simulated and assigned with time‐dependent DFT (TDDFT).