Electronic Structure and Spectroscopic Properties of Group-7 Tri-Oxo-Halides MO3X (M = Mn-Bh, X = F-Ts).
Xue-Lian JiangCong-Qiao XuJun-Bo LuChang-Su CaoHubert SchmidbaurW H Eugen SchwarzJun LiPublished in: Inorganic chemistry (2021)
The 24 trioxide halide molecules MO3X of the manganese group (M = Mn-Bh; X = F-Ts), which are iso-valence-electronic with the famous MnO4- ion, have been quantum-chemically investigated by quasi-relativistic density-functional and ab initio correlated approaches. Geometric and electronic structures, valence and oxidation numbers, vibrational and electronic spectral properties, energetic stabilities of the monomers in the gas phase, and the decay mode of MnO3F have been investigated. The light Mn-3d species are most strongly electron-correlated, indicating that the concept of a closed-shell Lewis-type single-configurational structure [Mn+7(d0) O-2(p6)3 F-(p6)] reaches its limits. The concept of real-valued spin orbitals φ(r)·α and φ(r)·β breaks down for the heavy Bh-6d, At-6p and Ts-7p elements because of the dominating spin-orbit coupling. The vigorous decomposition of MnO3F at ambient conditions starts by the autocatalyzed release of n O2 and the formation of MnmO3m-2nFm clusters, triggered by the electron-depleted "oxylic" character of the oxide ligands in MnO3X.
Keyphrases
- room temperature
- transition metal
- density functional theory
- molecular dynamics
- ionic liquid
- metal organic framework
- atomic force microscopy
- physical activity
- electron transfer
- air pollution
- solar cells
- optical coherence tomography
- molecular docking
- particulate matter
- single molecule
- molecular dynamics simulations
- nitric oxide
- magnetic resonance imaging
- computed tomography