Paper: Nitrogen splitting

Splitting N2 is a challenging undertaking due to the strong triple bond holding the two nitrogen atoms together. Traditionally, this task is achieved via the Haber-Bosch process but recently interest has shifted to the possibilities of nitrogen splitting via homogeneous catalysis. Computations on the dinuclear transition metal complexes involved can be performed thanks to modern computational hardware and appropriate computer codes. However, the analysis of the excited states involved can become a significant challenge due to the large number of states and difficulties in assigning their character unambiguously. To tackle this problem, we have recently devised a strategy for a detailed analysis of the electronic wavefunctions of the states contributing to the reactive process. The associated paper, led by S. Rupp and V. Krewald from TU Darmstadt, just appeared in the European Journal of Inorganic Chemistry: Multi‐tier electronic structure analysis of Sita’s Mo and W complexes capable of thermal or photochemical N2 splitting.

TheoDORE – Tutorial

An updated version of the tutorial for the TheoDORE wavefunction analysis program is ready, thanks to Patrick. The tutorial can be downloaded here:

For the newest version of the code go here:

In the tutorial, we explain the process of creating conditional electron densities for visualising electron correlation (ChemPhotoChem 2019, 3, 702). The figure below shows a comparison between the ionic and covalent singlet and triplet B3u states of naphthalene.

The tutorial also explains the creation of bar graphs for a compact representation of excited-state character (see Coord. Chem. Rev., 2018, 361, 74 and ChemRxiv.11395314). In the picture below, the excited states of an iridium complex are decomposed into metal-to-ligand charge transfer (MLCT), ligand-to-ligand charge transfer (LLCT), and ligand centred (LC) contributions. The lowest six states are all dominated by MLCT character but the presented analysis clearly shows that the first three have enhanced LC character compared to the latter three.