Reappraisal of cis effect in 1,2-dihaloethenes: an improved virtual orbital multireference approach

The Journal of Chemical Physics
Rajat K ChaudhuriUttam Sinha Mahapatra

Abstract

Computed relative stabilities for isomers of 1,2-difluoroethene and 1,2-dichloroethene isomers are compared with predictions based on chemical hardness (eta) and electrophilicity (omega) using the principles of maximum hardness and minimum electrophilicity. The chemical hardness and electrophilicity deduced either from improved virtual orbital (IVO) energies or from correlated treatments correctly predict that cis 1,2-difluoroethene and 1,2-dichloroethene are energetically more stable than the corresponding trans isomers, and the ground state energies from multireference perturbation theory with IVO orbitals agree with these predictions. However, when the same quantities are computed using Hartree-Fock orbitals, serious inconsistencies between the two approaches emerge in predicting the stability of the isomers of the 1,2-dihaloethenes. The present study clearly demonstrates that the IVO energies are appropriate for the computation of hardness related parameters, notably the chemical hardness and electrophilicity. Moreover, the IVO methods also provide smooth potential energy curves for the cis-trans isomerization of the two 1,2-dihaloethenes.

References

Sep 30, 1998·Proceedings of the National Academy of Sciences of the United States of America·A T MaynardD G Covell
Jul 21, 2004·The Journal of Chemical Physics·Monika Musiał, Rodney J Bartlett
Mar 3, 2005·The Journal of Chemical Physics·Caroline M TaylorKarl F Freed
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Sep 11, 2003·The Journal of Physical Chemistry. a·Eduardo ChamorroPatricio Fuentealba

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Citations

Jan 7, 2009·The Journal of Chemical Physics·Sudip ChattopadhyayUttam Sinha Mahapatra
Jan 15, 2009·The Journal of Chemical Physics·Uttam Sinha MahapatraRajat K Chaudhuri
Apr 22, 2017·Angewandte Chemie·Dayne C GeorgiouJason L Dutton
May 15, 2009·Physical Chemistry Chemical Physics : PCCP·Vincenzo BaroneGiacomo Prampolini
Mar 23, 2011·Physical Chemistry Chemical Physics : PCCP·Sudip ChattopadhyayKarl F Freed
Feb 16, 2010·The Journal of Physical Chemistry. a·Uttam Sinha MahapatraRajat K Chaudhuri
May 24, 2019·The Journal of Physical Chemistry. a·Kazuaki TokuhashiShigeo Kondo

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Software Mentioned

GAMESS
CR
MRMP
IVO
CC

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