Revisiting the Fundamental Nature of Metal‐Ligand Bonding: An Impartial and Automated Fitting Procedure for Angular Overlap Model Parameters

Abstract

The properties and reactivities of transition metal complexes are often discussed in terms of Ligand Field Theory (LFT), and with ab initio LFT a direct connection to quantum chemical wavefunctions was recently established. The Angular Overlap Model (AOM) is a widely used, ligandspecific parameterization scheme of the ligand field splitting that has, however, been restricted by the availability and resolution of experimental data. Using ab initio LFT, we present here a generalised, symmetry-independent and automated fitting procedure for AOM parameters that is even applicable to formally underdetermined or experimentally inaccessible systems. This method allows quantitative evalua-tions of assumptions commonly made in AOM applications, for example, transferability or the relative magnitudes of AOM parameters, and the response of the ligand field to structural or electronic changes. A two-dimensional spectrochemical series of tetrahedral halido metalates ([M II X 4 ] 2À , M = MnÀ Cu) served as a case study. A previously unknown linear relationship between the halide ligands' chemical hardness and their AOM parameters was found. The impartial and automated procedure for identifying AOM parameters introduced here can be used to systematically improve our understanding of ligand-metal interactions in coordination complexes.

On the potentially transformative role of auxiliary-field quantum Monte Carlo in quantum chemistry: A highly accurate method for transition metals and beyond

“…The fundamental reason is a lack of accurate reference data in systems with d and f electrons, which becomes a bottleneck despite machine learning advances and progress in molecular mechanics-inspired potentials. 18,19 This is, in part, a consequence of the scarcity of reliable, gas-phase experimental data (though progress in experimental techniques is encouraging 20 ), and reported measurements often are accompanied by large uncertainties. Meanwhile, the computational cost of exact theoretical approaches that in principle could yield predictions of quality comparable to experiments scales exponentially with system size.…”