Implicit and explicit host effects on excitons in pentacene derivatives

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Title: Implicit and explicit host effects on excitons in pentacene derivatives
Author(s): Charlton, RJ
Fogarty, R
Bogatko, S
Zuehlsdorff, TJ
Hine, NDM
Heeney, MJ
Horsfield, AP
Haynes, PD
Item Type: Journal Article
Abstract: An ab initio study of the effects of implicit and explicit hosts on the excited state properties of pentacene and its nitrogen-based derivatives has been performed using ground state density func- tional theory (DFT), time-dependent DFT and ∆SCF. We observe a significant solvatochromic redshift in the excitation energy of the lowest singlet state (S 1 ) of pentacene from inclusion in a p -terphenyl host compared to vacuum; for an explicit host consisting of six nearest neighbour p -terphenyls, we obtain a redshift of 65 meV while a conductor-like polarisable continuum model (CPCM) yields a 78 meV redshift. Comparison is made between the excitonic properties of pen- tacene and four of its nitrogen-based analogues, 1,8-, 2,9-, 5,12-, and 6,13-diazapentacene with the latter found to be the most distinct due to local distortions in the ground state electronic struc- ture. We observe that a CPCM is insufficient to fully understand the impact of the host due to the presence of a mild charge-transfer (CT) coupling between the chromophore and neighbouring p -terphenyls, a phenomenon which can only be captured using an explicit model. The strength of this CT interaction increases as the nitrogens are brought closer to the central acene ring of pentacene.
Publication Date: 14-Mar-2018
Date of Acceptance: 20-Feb-2018
URI: http://hdl.handle.net/10044/1/57458
DOI: https://dx.doi.org/10.1063/1.5017285
ISSN: 0021-9606
Publisher: AIP Publishing
Journal / Book Title: Journal of Chemical Physics
Volume: 148
Issue: 10
Sponsor/Funder: Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
The Leverhulme Trust
Engineering and Physical Sciences Research Council
Engineering and Physical Sciences Research Council
Engineering & Physical Science Research Council (E
Funder's Grant Number: EP/J015059/1
EP/K011987/1
RPG-2014-125
EP/L015579/1
EP/L015579/1
EP/P02209X/1
Copyright Statement: © 2018 The Author(s). Published by AIP Publishing. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in Journal of Chemical Physics and may be found at https://aip.scitation.org/doi/10.1063/1.5017285
Keywords: Science & Technology
Physical Sciences
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
Chemistry
Physics
DENSITY-FUNCTIONAL THEORY
SINGLET FISSION
ELECTRONIC EXCITATIONS
STATES
QUANTUM
MOLECULES
SYSTEMS
CHARGE
ACENES
APPROXIMATION
02 Physical Sciences
03 Chemical Sciences
09 Engineering
Chemical Physics
Publication Status: Published
Article Number: 104108
Online Publication Date: 2018-03-12
Appears in Collections:Faculty of Engineering
Materials
Chemistry
Faculty of Natural Sciences



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