Chemical Bonding in Open‐Shell Transition‐Metal Complexes

On the multi-reference nature of plutonium oxides: PuO22+, PuO2, PuO3 and PuO2(OH)2

“…Furthermore, when combined with concepts of quantum information theory, DMRG allows us to quantify orbital entanglement [32] and orbital-pair correlations [30,[33][34][35][36][37][38][39] that enable us to gain a better understanding of electron correlation effects, [36,40,41] elucidate chemical bonding in molecules, [37,[42][43][44][45][46][47] and detect changes in the electronic wave function. [48][49][50] The suitability of DMRG for helping to understand the electronic structure of actinides can be seen in a recent study of the changes in the ground-state for the CUO molecule when diluted in different noble gas matrices.…”

Resolving the π-assisted U–N σf-bond formation using quantum information theory

“…84,87 The single-orbital entropy and orbital-pair mutual information allow us to elucidate the strength of orbital correlations, resolve qualitative changes in the wave function, and monitor the formation (or breaking) of individual bonds in complex molecules along a reaction pathway. 44,46,92,93 Examples include physical model systems, 84,87 first-row elements, 43,81 transitionmetal complexes, 44,45,80,94,95 and actinide chemistry. 11,46,92,96 In this work, we focus on the U-N s f -bond formation process.…”

The effect of nitrido, azide, and nitrosyl ligands on magnetization densities and magnetic properties of iridium PNP pincer-type complexes

“…27,28 Computationally cheap methods such as DFT, oen fail in predicting the energetically lowest-lying spin-state electronic conguration and spin-density distributions in open-shell transition-metal complexes. 23,24,[29][30][31][32][33][34][35][36][37] Failures of approximate exchange-correlation functionals in predicting molecular properties of open-shell complexes have been traced to the delocalization error and static correlation error, 38,39 which are rooted in an inappropriate behavior of the energy with respect to fractional charges and fractional spins. [40][41][42][43][44] Reliable modeling of transition metal compounds requires more expensive, but robust wavefunction-based methods that can further be used to assess the accuracy and reliability of DFT calculations.…”

“…They function as π accepting, noninnocent ancillary ligands and take the form of either the linear or bent transformations. 23,24,[29][30][31][32][33][34][35][36][37] Failures of approximate exchange-correlation functionals in predicting molecular properties of open-shell complexes have been traced to the delocalization error and static correlation error, 38,39 which are rooted in an inappropriate behavior of the energy with respect to fractional charges and fractional spins. The non-innocence of this ligand allows it to stabilize various species involved in catalysis by either supplying electron density to the metal center or scavenging electrons located on the metal center.…”