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Diboron- and Diaza-Doped Anthracenes and Phenanthrenes: Their Electronic Structures for Being Singlet Fission Chromophores

Pradhan, Ekadashi and Lee, Seunghoon and Choi, Cheol Ho and Zeng, Tao (2020) Diboron- and Diaza-Doped Anthracenes and Phenanthrenes: Their Electronic Structures for Being Singlet Fission Chromophores. Journal of Physical Chemistry A, 124 (40). pp. 8159-8172. ISSN 1089-5639. https://resolver.caltech.edu/CaltechAUTHORS:20200911-133137193

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Abstract

We used quantum chemistry methods at the levels of mixed-reference spin-flip time-dependent density functional theory and multireference perturbation theory to study diboron- and diaza-doped anthracenes and phenanthrenes. This class of structures recently surged as potential singlet fission chromophores. We studied electronic structures of their excited states and clarified the reasons why they satisfy or fail to satisfy the energy criteria for singlet fission chromophores. Many studied structures have their S₁ states not dominated by HOMO → LUMO excitation, so they cannot be described using the conventional two site model. This is attributed to frontier orbital energy shifts induced by the doping and different charge-transfer energies in different one-electron singlet excitations or, in other words, different polarizations of hole and/or particle orbitals in their S₁ and T₁ states. There is a mirror relation between the orbital energy shifts induced by diboron- and diaza-dopings, which together with alternant hydrocarbon pairings of occupied and unoccupied orbitals, leads to more mirror relations between the excited states of the two types of doped structures.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jpca.0c06915DOIArticle
ORCID:
AuthorORCID
Choi, Cheol Ho0000-0002-8757-1396
Zeng, Tao0000-0002-1553-7850
Additional Information:© 2020 American Chemical Society. Received: July 28, 2020; Revised: September 7, 2020; Published: September 9, 2020. We thank York University for the start-up grant (T.Z.: 481333) and the Natural Sciences and Engineering Research Council (NSERC) of Canada (T.Z.: RGPIN-2016-06276) for financial support. We thank the Neese group at the University of Bonn for their continuous development of the ORCA program package. We thank the Gordon group at the Iowa State University for their continuous development of the GAMESS-US program package. This research was enabled in part by support provided by WestGrid (www.westgrid.ca), SciNet (www.scinethpc.ca), and Compute Canada (www.computecanada.ca). The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
York University481333
Natural Sciences and Engineering Research Council of Canada (NSERC)RGPIN-2016-06276
WestGridUNSPECIFIED
SciNetUNSPECIFIED
Compute CanadaUNSPECIFIED
Issue or Number:40
Record Number:CaltechAUTHORS:20200911-133137193
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200911-133137193
Official Citation:Diboron- and Diaza-Doped Anthracenes and Phenanthrenes: Their Electronic Structures for Being Singlet Fission Chromophores. Ekadashi Pradhan, Seunghoon Lee, Cheol Ho Choi, and Tao Zeng. The Journal of Physical Chemistry A 2020 124 (40), 8159-8172; DOI: 10.1021/acs.jpca.0c06915
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:105347
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:14 Sep 2020 14:14
Last Modified:21 Oct 2020 16:36

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