Alternative mechanisms of the primary act of gas-phase monomolecular thermal decomposition of N-methyl-N’-methoxydiazene-N-oxide according to the data of quantum chemical calculations

The mechanisms of the primary act of thermal decomposition of the simplest representative of the series of alkoxy-NNO-azoxy compounds – N-methyl-N’-methoxydiazene-N- oxide are studied using quantum-chemical density functional methods PBE, B3LYP, wB97XD with different sets of basic functions, as well as the composite G4 method. It is shown that the most probable channel of its thermal destruction, leading to the formation of experimentally observed reaction products, is isomerization because of rotation of the OCH3 group around the NO bond with the subsequent transfer of the CH3 group between oxygen atoms. In this case, the transfer of the CH3 group is the limiting reaction of the thermal decomposition of N-methyl-N’-methoxydiazene-N-oxide as a whole.

[(VIVO)2MII5] (M = Ni, Co) Anderson Wheels

Heterometallic Anderson wheels of formula [(VIVO)2MII5(hmp)10Cl2](ClO4)2·2MeOH (M = Ni, 1; Co, 2) have been synthesised from the solvothermal reaction of M(ClO4)2·6H2O and VCl3 with hmpH (2-(hydroxymethyl)pyridine). The metallic skeleton describes a centred hexagon, with the two vanadyl ions sitting on opposing sides of the outer ring. Magnetic susceptibility and magnetisation measurements indicate the presence of both ferromagnetic and antiferromagnetic exchange interactions. Theoretical calculations based on density functional methods reproduce both the sign and strength of the exchange interactions found experimentally, and rationalise the parameters extracted.

[(VIVO)2MII5] (M = Ni, Co) Anderson Wheels

Heterometallic Anderson wheels of formula [(VIVO)2MII5(hmp)10Cl2](ClO4)2·2MeOH (M = Ni, 1; Co, 2) have been synthesised from the solvothermal reaction of M(ClO4)2·6H2O and VCl3 with hmpH (2-(hydroxymethyl)pyridine). The metallic skeleton describes a centred hexagon, with the two vanadyl ions sitting on opposing sides of the outer ring. Magnetic susceptibility and magnetisation measurements indicate the presence of both ferromagnetic and antiferromagnetic exchange interactions. Theoretical calculations based on density functional methods reproduce both the sign and strength of the exchange interactions found experimentally, and rationalise the parameters extracted.

Accurate calculation of spin-state energy gaps in Fe(III) Spin-Crossover systems using Density Functional Methods

Fe(III) complexes are receiving ever-increasing attention as spin crossover (SCO) systems because they are usually air stable, as opposed to Fe(II) complexes, which are prone to oxidation. Here, we present...

Lieb–Oxford bound and pair correlation functions for density-functional methods based on the adiabatic-connection fluctuation-dissipation theorem

Compliance with the Lieb–Oxford bound is investigated for density-functional methods based on the ACFD theorem to treat correlation. Correlation pair densities resulting from such methods are compared with highly accurate reference values.