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The cis-effect explained using next generation QTAIM

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Peng_2022_The_cis_effect_explained_Molecules_27_18_06099_CCBY.pdf (1.460Mb)
Date
18/09/2022
Author
Peng, Yuting
Yu, Wenjing
Feng, Xinxin
Xu, Tianlv
Früchtl, Herbert
van Mourik, Tanja
Kirk, Steven R.
Jenkins, Samantha
Keywords
QTAIM
NG-QTAIM
cis effect
Dihaloethene
Dihalodiazene
QD Chemistry
T-DAS
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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.
Citation
Peng , Y , Yu , W , Feng , X , Xu , T , Früchtl , H , van Mourik , T , Kirk , S R & Jenkins , S 2022 , ' The cis -effect explained using next generation QTAIM ' , Molecules , vol. 27 , no. 18 , 6099 . https://doi.org/10.3390/molecules27186099
Publication
Molecules
Status
Peer reviewed
DOI
https://doi.org/10.3390/molecules27186099
ISSN
1420-3049
Type
Journal article
Rights
Copyright: © 2022 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/4.0/).
Description
The National Natural Science Foundation of China is gratefully acknowledged, project approval number: 21673071. The One Hundred Talents Foundation of Hunan Province is also gratefully acknowledged for the support of S.J. and S.R.K. H.F. and T.v.M. gratefully acknowledge computational support via the EaStCHEM Research Computing Facility.
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  • University of St Andrews Research
URI
http://hdl.handle.net/10023/26047

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