What governs magnetic exchange couplings in radical-bridged dinuclear complexes?

Coupling transition metal or lanthanide ions through a radical bridging ligand is a promising route to increase performances in the area of single molecular magnets. A better understanding of the underlying physical mechanisms governing the magnetic exchange couplings is thus of valuable importance to design future compounds. Here, couplings in three series of metal-radical-metal compounds based on transition metal ions are investigated by means of the decomposition/recomposition methods. This work presents the generalisation and first application of the method to systems with an arbitrary number of magnetic centres featuring several unpaired electrons. Thanks to the decomposition into the three main contributions (direct exchange, kinetic exchange, and spin polarisation) as well as a description in terms of electron-electron interactions, we study the influence of the nature of the metal centre and the radical ligand on the couplings. We combine the energetic contributions extracted with orbital and charge population analysis to rationalise the results.

Ionic Conductivity and Structure of Glasses Synthesized by Mechanical-Milling Methods in the x[Na2S]-(100 - x) [0.5GeS2-0.5Ga2S3] System.

Chalcogenide glasses in the Na2S-GeS2-Ga2S3 pseudoternary system were synthesized using a combination route of melt-quenching and mechanical-milling methods. First, a glass rich in germanium (90GeS2-10Ga2S3) is synthesized by melt-quenching synthesis in a silica tube sealed under vacuum. This glass is used as a precursor for the second step of mechanochemistry to explore the Na2S-GeS2-Ga2S3 pseudoternary system. By using this synthesis route, the glass-forming ability is improved as the vitreous domain is enlarged, especially for Na- and Ga-rich compositions. The as-obtained amorphous powders are characterized by Raman spectroscopy, differential scanning calorimetry, X-ray total scattering, and pair distribution function (PDF) analysis. The evolution of the Raman features observed is reproduced using density functional theory calculations. Impedance spectroscopy was performed to determine the conductivity of the new glasses. The addition of germanium sulfide to the Na2S-Ga2S3 pseudobinary system enables one to increase the conductivity by 1 order of magnitude. The highest room-temperature ionic conductivity, as measured by impedance spectroscopy, is 1.8 × 10-5 S·cm-1.

Revisiting magnetic exchange couplings in heterodinuclear complexes through the decomposition method in KS-DFT.

Providing tools to understand the physical mechanisms governing magnetic properties in transition metal-based compounds is still of great interest. Here, the magnetic exchange coupling in a series of heterodinuclear complexes is investigated by means of the decomposition method. This work presents the first application of the decomposition method to systems where magnetic centres may bear more than one unpaired electron. By decomposing the coupling into three physical contributions (direct exchange, kinetic exchange, and spin polarisation), we provide numerical arguments to confirm or infirm the rationalisation allowed by the conceptual analysis of the magnetic d orbitals. We also take advantage of the recently proposed generalisation of the method [David et al., J. Chem. Theory Comput., 2023, 19, 157] to get more insights into the underlying mechanisms by disentangling the coupling between centres into its electron-electron interactions.

Evaluation of tight-binding DFT performance for the description of organic photochromes properties.

Photochromic molecules are widely studied and developed for their many potential applications. To optimize the required properties through theoretical models, a considerable chemical space is to be explored, and their environment in devices is to be accounted for.. To this end, cheap and reliable computational methods can be powerful tools to steer synthetic developments. As ab initio methods remain costly for extensive studies (in terms of the size of the system and/or number of molecules), semiempirical methods such as density functional tight-binding (TB) could offer a good compromise between accuracy computational cost. However, these approaches necessitate benchmarking on the families of compounds of interest. Thus, the aim of the present study is to evaluate the accuracy of several key features calculated with TB methods (DFTB2, DFTB3, GFN2-xTB, and LC-DFTB2) for three sets of photochromic organic molecules: azobenzene (AZO), norbornadiene/quadricyclane (NBD/QC), and dithienylethene (DTE) derivatives. The features considered here are the optimized geometries, the difference in energy between the two isomers (ΔE), and of the energies of the first relevant excited states. All the TB results are compared to those obtained with DFT methods and state-of-the-art electronic structure calculation methods: DLPNO-CCSD(T) for ground states and DLPNO-STEOM-CCSD for excited states. Our results show that, overall, DFTB3 is the TB method leading to the best results for the geometries and the ΔE values and can be used alone for these purposes for NBD/QC and DTE derivatives. Single point calculations at the r2SCAN-3c level using TB geometries allow circumventing the deficiencies of the TB methods in the AZO series. For electronic transition calculations, the range separated LC-DFTB2 method is the most accurate TB method tested for AZO and NBD/QC derivatives, in close agreement with the reference.