Relation Between Ring Currents and Hydrogenation Enthalpies for Assessing the Degree of Aromaticity

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Kumar , C , Fliegl , H & Sundholm , D 2017 , ' Relation Between Ring Currents and Hydrogenation Enthalpies for Assessing the Degree of Aromaticity ' , Journal of Physical Chemistry A , vol. 121 , no. 38 , pp. 7282-7289 . https://doi.org/10.1021/acs.jpca.7b07607

Title: Relation Between Ring Currents and Hydrogenation Enthalpies for Assessing the Degree of Aromaticity
Author: Kumar, Chandan; Fliegl, Heike; Sundholm, Dage
Contributor organization: Department of Chemistry
Date: 2017-09-28
Language: eng
Number of pages: 8
Belongs to series: Journal of Physical Chemistry A
ISSN: 1089-5639
DOI: https://doi.org/10.1021/acs.jpca.7b07607
URI: http://hdl.handle.net/10138/309501
Abstract: Magnetically induced ring-current strength susceptibilities and nucleus independent chemical shifts (NICS) have been studied for 15 single-ring aromatic, antiaromatic, and nonaromatic molecules. The current densities have been calculated at the density functional theory (DFT), Hartree-Fock (HF) theory, and second-order Moller-Plesset perturbation theory (MP2) levels using the gauge-including magnetically induced current method (GIMIC). The ring-current strength susceptibilities have been obtained by numerical integration of the current density flowing around the molecular ring. The calculated ring-current strength susceptibilities are almost independent of the level of theory. The relative degree of aromaticity deduced from the magnetic properties has been compared with the ones deduced from hydrogenation enthalpies that are considered to be proportional to aromatic stabilization energies (ASE). For the studied single-ring molecules, GIMIC, NICS, and ASE calculations yield similar trends. The study shows that there is a linear correlation between the magnetic and energetic criteria of aromaticity. The largest uncertainty originates from the accuracy of the energy data, because they are much more dependent on the employed computational level than the calculated magnetic properties. Thus, ring-current strength susceptibilities can be used for assessing the degree of aromaticity.
Subject: INDUCED CURRENT-DENSITY
INDEPENDENT CHEMICAL-SHIFTS
MAGNETICALLY INDUCED CURRENTS
INCLUDING ATOMIC ORBITALS
ZETA VALENCE QUALITY
CURRENT MODEL
BASIS-SETS
CONTINUOUS TRANSFORMATION
ELECTRON DELOCALIZATION
ANTIAROMATIC CHARACTER
116 Chemical sciences
114 Physical sciences
Peer reviewed: Yes
Rights: unspecified
Usage restriction: openAccess
Self-archived version: acceptedVersion


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