The cis-effect explained using next generation QTAIM

Yuting Peng, Wenjing Yu, Xinxin Feng, Tianlv Xu, Herbert Früchtl, Tanja van Mourik*, Steven R. Kirk, Samantha Jenkins*

*Corresponding author for this work

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Abstract

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 Tσ(s) used to sample the Uσ-space cis- and trans-characteristics. The Tσ(s) were constructed by subjecting the C1-C2 BCP and N1-N2 BCP to torsions ± θ and summing all possible Tσ(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 Tσ(s) with cis- and trans-characteristics, respectively, based on the relative ease of motion of the electronic charge density ρ(rb). Qualitative agreement is found with existing experimental data and predictions are made where experimental data is not available.
Original languageEnglish
Article number6099
JournalMolecules
Volume27
Issue number18
DOIs
Publication statusPublished - 18 Sept 2022

Keywords

  • QTAIM
  • NG-QTAIM
  • cis effect
  • Dihaloethene
  • Dihalodiazene

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