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A DFT Insight on L n Pu + (L = C 4 H 4 , C 5 H 5 , C 6 H 6 ; n = 1–3) Complexes: Nature of Interactions and Electronic Spectroscopy
Author(s) -
Du Jiguang,
Jiang Gang
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201501412
Subject(s) - chemistry , electron localization function , delocalized electron , chemical bond , atomic orbital , covalent bond , crystallography , molecule , spectral line , atoms in molecules , chemical shift , natural bond orbital , electron , density functional theory , computational chemistry , atomic physics , physics , astronomy , organic chemistry , quantum mechanics
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 + C 5 H 5 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.