Strategies to Calculate Fukui Functions and Applications to Radicals with SOMO-HOMO Inversion.

This work explores an efficient and numerically accurate procedure to obtain the Fukui function from fractional orbital occupation calculations. The energy- and density-linearity conditions are investigated in the context of using optimally tuned range-separated hybrid functionals for the calculation of the Fukui function. The methodology is then used to study the reactivity of organic radicals exhibiting energetic inversion between the singly occupied molecular orbital (SOMO) and the highest occupied molecular orbital (HOMO), that is, SOMO-HOMO inversion (SHI).

Experimental and Computational Determination of a M-Cl Homolytic Bond Dissociation Free Energy: Mn(III)Cl-Mediated C-H Cleavage and Chlorination.

This study confirms the hypothesis that [MnCl(OPPh)] () and acetonitrile-solvated MnCl (i.e., [MnCl(MeCN)]) can be used as synthons to prepare Mn(III) chloride complexes with facially coordinating ligands.

Density-Corrected Density Functional Theory for Molecular Properties.

Density-corrected (DC) density functional theory (DFT) has been proposed to overcome difficulties related to the self-interaction error. The procedure uses the Hartree-Fock electron density (matrix) non-self-consistently in conjunction with an approximate functional. DC-DFT has so far mainly been tested for total energy differences, whereas other types of molecular properties have not been evaluated systematically.

Comparison of the Performance of Density Functional Methods for the Description of Spin States and Binding Energies of Porphyrins.

This work analyzes the performance of 250 electronic structure theory methods (including 240 density functional approximations) for the description of spin states and the binding properties of iron, manganese, and cobalt porphyrins. The assessment employs the Por21 database of high-level computational data (CASPT2 reference energies taken from the literature). Results show that current approximations fail to achieve the "chemical accuracy" target of 1.

Low-Temperature Luminescence in Organic Helicenes: Singlet versus Triplet State Circularly Polarized Emission.

The experimental measurement of the photophysical and chiroptical properties of helicene-based π-conjugated emitters with electron-accepting (-CN, -py, -NO) or donating (TMS, NMe, NH) moieties is reported at low temperature (77 K). The samples exhibit strong circularly polarized phosphorescence in frozen solution of 2-MeTHF, with a luminescence dissymmetry factor reaching 1.6 × 10 and a lifetime of over 0.