Dickens, T.K. orcid.org/0000-0003-0342-3597, Mallion, R.B. orcid.org/0000-0002-3642-269X, Fowler, P.W. orcid.org/0000-0003-2106-1104 et al. (2 more authors) (2024) Ring currents in the clar goblet calculated using configurational state averaging. The Journal of Physical Chemistry A, 128 (47). pp. 10181-10192. ISSN 1089-5639
Abstract
The closed-shell Hückel-London-Pople-McWeeny formalism for ring currents is extended to Aufbau configurations with open shells calculated as configurational averages. The method is applied to the non-Kekulean benzenoid known as the Clar goblet, recently synthesized on the Au(111) surface. Multiplicity of the ground state is a complication: for the Clar goblet, Hund’s rule of maximum multiplicity implies a triplet whereas Ovchinnikov’s rule implies a singlet. This disagreement has little effect on the predicted ring currents. Ring-current maps are calculated for the 36π dication, 40π dianion, and low-lying states of the 38π neutral, using Hückel-London and Hubbard-London models. All show twin diatropic perimeter currents on separate halves of the molecule. These are compared with ipsocentric pseudo-π and ab initio maps of induced π-current for closed-shell singlet configurations of dianion, dication, and neutral. Configurationally averaged Hückel-London calculations give a good account of the consistent diatropic ring currents in the Clar goblet for the three charge states.
Metadata
Item Type: | Article |
---|---|
Authors/Creators: |
|
Copyright, Publisher and Additional Information: | © 2024 The Authors. This is an Open Access article distributed under the terms of the Creative Commons Attribution Licence (https://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. |
Dates: |
|
Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) The University of Sheffield > Faculty of Science (Sheffield) > School of Mathematical and Physical Sciences |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 12 Dec 2024 10:23 |
Last Modified: | 12 Dec 2024 10:23 |
Published Version: | http://dx.doi.org/10.1021/acs.jpca.4c05393 |
Status: | Published |
Publisher: | American Chemical Society (ACS) |
Refereed: | Yes |
Identification Number: | 10.1021/acs.jpca.4c05393 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:220342 |