Non-Covalent Interactions and Impact of Charge Penetration Effects in Linear Oligoacene Dimers and Single Crystals

Handle URI:
http://hdl.handle.net/10754/610609
Title:
Non-Covalent Interactions and Impact of Charge Penetration Effects in Linear Oligoacene Dimers and Single Crystals
Authors:
Ryno, Sean M; Risko, Chad; Bredas, Jean-Luc ( 0000-0001-7278-4471 )
Abstract:
Non-covalent interactions determine in large part the thermodynamic aspects of molecular packing in organic crystals. Using a combination of symmetry-adapted perturbation theory (SAPT) and classical multipole electrostatics, we describe the interaction potential energy surfaces for dimers of the oligoacene family, from benzene to hexacene. An analysis of these surfaces and a thorough assessment of dimers extracted from the reported crystal structures underline that high-order interactions (i.e., three-body non-additive interactions) must be considered in order to rationalize the details of the crystal structures. A comparison of the SAPT electrostatic energy with the multipole interaction energy demonstrates the importance of the contribution of charge penetration, which is shown to account for up to 50% of the total interaction energy in dimers extracted from the experimental single crystals; in the case of the most stable co-facial model dimers, this contribution is even larger than the total interaction energy. Our results highlight the importance of taking account of charge penetration in studies of the larger oligoacenes.
KAUST Department:
Solar and Photovoltaic Engineering Research Center (SPERC)
Citation:
Non-Covalent Interactions and Impact of Charge Penetration Effects in Linear Oligoacene Dimers and Single Crystals 2016 Chemistry of Materials
Publisher:
American Chemical Society (ACS)
Journal:
Chemistry of Materials
Issue Date:
18-May-2016
DOI:
10.1021/acs.chemmater.6b01340
Type:
Article
ISSN:
0897-4756; 1520-5002
Sponsors:
This work has been supported by King Abdullah University of Science and Technology (KAUST), the KAUST Competitive Research Grant program, and the Office of Naval Research Global (Award N62909-15-1-2003). We acknowledge the IT Research Computing Team and Supercomputing Laboratory at KAUST for providing computational and storage resources. This work has also used the computing resources of the Garnet, Spirit, and Copper supercomputing systems through the DoD HPCMP. We wish to thank Prof. C. David Sherrill, Dr. Rob Parrish, and Mr. Trent Parker for technical assistance and stimulating discussions.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acs.chemmater.6b01340
Appears in Collections:
Articles; Solar and Photovoltaic Engineering Research Center (SPERC)

Full metadata record

DC FieldValue Language
dc.contributor.authorRyno, Sean Men
dc.contributor.authorRisko, Chaden
dc.contributor.authorBredas, Jean-Lucen
dc.date.accessioned2016-05-24T12:13:45Z-
dc.date.available2016-05-24T12:13:45Z-
dc.date.issued2016-05-18-
dc.identifier.citationNon-Covalent Interactions and Impact of Charge Penetration Effects in Linear Oligoacene Dimers and Single Crystals 2016 Chemistry of Materialsen
dc.identifier.issn0897-4756-
dc.identifier.issn1520-5002-
dc.identifier.doi10.1021/acs.chemmater.6b01340-
dc.identifier.urihttp://hdl.handle.net/10754/610609-
dc.description.abstractNon-covalent interactions determine in large part the thermodynamic aspects of molecular packing in organic crystals. Using a combination of symmetry-adapted perturbation theory (SAPT) and classical multipole electrostatics, we describe the interaction potential energy surfaces for dimers of the oligoacene family, from benzene to hexacene. An analysis of these surfaces and a thorough assessment of dimers extracted from the reported crystal structures underline that high-order interactions (i.e., three-body non-additive interactions) must be considered in order to rationalize the details of the crystal structures. A comparison of the SAPT electrostatic energy with the multipole interaction energy demonstrates the importance of the contribution of charge penetration, which is shown to account for up to 50% of the total interaction energy in dimers extracted from the experimental single crystals; in the case of the most stable co-facial model dimers, this contribution is even larger than the total interaction energy. Our results highlight the importance of taking account of charge penetration in studies of the larger oligoacenes.en
dc.description.sponsorshipThis work has been supported by King Abdullah University of Science and Technology (KAUST), the KAUST Competitive Research Grant program, and the Office of Naval Research Global (Award N62909-15-1-2003). We acknowledge the IT Research Computing Team and Supercomputing Laboratory at KAUST for providing computational and storage resources. This work has also used the computing resources of the Garnet, Spirit, and Copper supercomputing systems through the DoD HPCMP. We wish to thank Prof. C. David Sherrill, Dr. Rob Parrish, and Mr. Trent Parker for technical assistance and stimulating discussions.en
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.chemmater.6b01340en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.chemmater.6b01340.en
dc.titleNon-Covalent Interactions and Impact of Charge Penetration Effects in Linear Oligoacene Dimers and Single Crystalsen
dc.typeArticleen
dc.contributor.departmentSolar and Photovoltaic Engineering Research Center (SPERC)en
dc.identifier.journalChemistry of Materialsen
dc.eprint.versionPost-printen
dc.contributor.institutionDepartment of Chemistry & Center for Applied Energy Research University of Kentucky Lexington, Kentucky 40506-0055en
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorRyno, Sean Men
kaust.authorBredas, Jean-Lucen
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.