Reaction barrier heights for cycloreversion of heterocyclic rings: An Achilles’ heel for DFT and standard ab initio procedures

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dc.contributor.authorYu, Li-Juan
dc.contributor.authorSarrami, Farzaneh
dc.contributor.authorO’Reilly, Robert J.
dc.contributor.authorKarton, Amir
dc.creatorLi-Juan, Yu
dc.date.accessioned2017-12-15T06:25:46Z
dc.date.available2017-12-15T06:25:46Z
dc.date.issued2015-09-08
dc.description.abstractAbstract We introduce a database of 20 accurate cycloreversion barrier heights of 5-membered heterocyclic rings (to be known as the CRBH20 database). In these reactions, dioxazole and oxathiazole rings are fragmented to form isocyanates, isothiocyanates, and carbonyls. The reference reaction barrier heights are obtained by means of the high-level, ab initio W1-F12 and W1w thermochemical protocols. We evaluate the performance of 65 contemporary density functional theory (DFT) and double-hybrid DFT (DHDFT) procedures. The CRBH20 database represents an extremely challenging test for these methods. Most of the conventional DFT functionals (74%) result in root-mean-square deviations (RMSDs) between 10 and 81kJmol−1. The rest of the DFT functionals attain RMSDs=5−10kJmol−1. Of the 12 tested DHDFT functionals, only five result in RMSDs<10kJmol−1. The CRBH20 dataset also proves to be a surprisingly challenging target for composite and standard ab initio procedures.en_US
dc.identifierDOI:10.1016/j.chemphys.2015.07.005
dc.identifier.citationLi-Juan Yu, Farzaneh Sarrami, Robert J. O’Reilly, Amir Karton, Reaction barrier heights for cycloreversion of heterocyclic rings: An Achilles’ heel for DFT and standard ab initio procedures, In Chemical Physics, Volume 458, 2015, Pages 1-8en_US
dc.identifier.issn03010104
dc.identifier.urihttps://www.sciencedirect.com/science/article/pii/S0301010415001895
dc.identifier.urihttp://nur.nu.edu.kz/handle/123456789/2944
dc.language.isoenen_US
dc.publisherChemical Physicsen_US
dc.relation.ispartofChemical Physics
dc.rights.licenseCopyright © 2015 Elsevier B.V. All rights reserved.
dc.subjectCycloreversionen_US
dc.subjectCycloeliminationen_US
dc.subjectDensity functional theoryen_US
dc.subjectG4 theoryen_US
dc.subjectW1 theoryen_US
dc.titleReaction barrier heights for cycloreversion of heterocyclic rings: An Achilles’ heel for DFT and standard ab initio proceduresen_US
dc.typeArticleen_US
elsevier.aggregationtypeJournal
elsevier.coverdate2015-09-08
elsevier.coverdisplaydate8 September 2015
elsevier.endingpage8
elsevier.identifier.doi10.1016/j.chemphys.2015.07.005
elsevier.identifier.eid1-s2.0-S0301010415001895
elsevier.identifier.piiS0301-0104(15)00189-5
elsevier.identifier.scopusid84989213968
elsevier.openaccess0
elsevier.openaccessarticlefalse
elsevier.openarchivearticlefalse
elsevier.startingpage1
elsevier.teaserWe introduce a database of 20 accurate cycloreversion barrier heights of 5-membered heterocyclic rings (to be known as the CRBH20 database). In these reactions, dioxazole and oxathiazole rings are fragmented...
elsevier.volume458
workflow.import.sourcescience

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