Inverted-sandwich-type and open-lantern-type dinuclear transition metal complexes: theoretical study of chemical bonds by electronic stress tensor

TL;DR

This study uses the electronic stress tensor to analyze and compare the chemical bonds in inverted-sandwich and open-lantern transition metal complexes, providing insights into bond strength and electronic structure.

Contribution

It introduces a novel bond order measure based on the electronic stress tensor and compares it with conventional methods, applying it to specific transition metal complexes.

Findings

Bond order correlates with MO-based results for metal-benzene bonds.

Energy density-based bond order effectively describes metal-metal bond strengths.

Stress tensor analysis reveals characteristic eigenvalue and eigenvector patterns.

Abstract

We study the electronic structure of two types of transition metal complexes, the inverted-sandwich-type and open-lantern-type, by the electronic stress tensor. In particular, the bond order b_e measured by the energy density which is defined from the electronic stress tensor is studied and compared with the conventional MO based bond order. We also examine the patterns found in the largest eigenvalue of the stress tensor and corresponding eigenvector field, the "spindle structure" and "pseudo-spindle structure". As for the inverted-sandwich-type complex, our bond order b_e calculation shows that relative strength of the metal-benzene bond among V, Cr and Mn complexes is V > Cr > Mn which is consistent with the MO based bond order. As for the open-lantern-type complex, we find that our energy density based bond order can properly describe the relative strength of Cr--Cr and Mo--Mo bonds by the surface integration of the energy density over the "Lagrange surface" which can take into account the spatial extent of the orbitals.