The Cis-Effect Explained Using Next-Generation QTAIM

We used next-generation QTAIM (NG-QTAIM) to explain the cis-effect for two families of molecules: C₂X₂ (X = H, F, Cl) and N₂X₂ (X = H, F, Cl). We explained why the cis-effect is the exception rather than the rule. This was undertaken by tracking the motion of the bond critical point (BCP) of the stress tensor trajectories T_σ(s) used to sample the U_σ-space cis- and trans-characteristics. The T_σ(s) were constructed by subjecting the C1-C2 BCP and N1-N2 BCP to torsions ± θ and summing all possible T_σ(s) from the bonding environment. During this process, care was taken to fully account for multi-reference effects. We associated bond-bending and bond-twisting components of the T_σ(s) with cis- and trans-characteristics, respectively, based on the relative ease of motion of the electronic charge density ρ(r). Qualitative agreement is found with existing experimental data and predictions are made where experimental data is not available.