Conformational preferences of diallylamine: A rotational spectroscopic and theoretical study

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dc.contributor.authorSilva, Weslley G. D. P.
dc.contributor.authorDaudet, Gabrielle
dc.contributor.authorPerez, Sem
dc.contributor.authorThorwirth, Sven
dc.contributor.authorvan Wijngaarden, Jennifer
dc.date.accessioned2021-10-26T18:00:07Z
dc.date.available2021-10-26T18:00:07Z
dc.date.issued2021-04-23
dc.date.submitted2021-10-26T17:11:07Zen_US
dc.description.abstractThe conformational space of diallylamine (DAA) was investigated using rotational spectroscopy from 7–19 GHz aided by quantum chemical calculations. Extensive conformational searches using density functional theory B3LYP-D3(BJ) and the ab initio MP2 method with the aug-cc-pVTZ basis set identified a total of 42 minima for DAA within ~22 kJ mol-1. This reveals a strikingly rich conformational landscape for this secondary amine with two equivalent substituents. Experimentally, transitions belonging to four low energy conformers (I, II, III and IV) were unequivocally assigned in the rotational spectrum and their patterns were confirmed by the presence of the hyperfine structure owing to the 14N quadrupolar nucleus. The relative intensities of the observed transitions suggest a conformational energy ordering of I < II < III < IV. Natural bond orbital and non-covalent interaction calculations reveal that the geometric preferences for the observed conformers are governed by an interplay of subtle attractive interactions (including hyperconjugation involving the lone pair at nitrogen) and repulsive effects.en_US
dc.description.sponsorshipNSERC RGPIN/0653-2016en_US
dc.identifier.citationSilva, W. G. D. P.; Daudet, G.; Perez, S.; Thorwirth, S.; van Wijngaarden, J. Conformational preferences of diallylamine: A rotational spectroscopic and theoretical study. J. Chem. Phys. 2021, 154, 164303.en_US
dc.identifier.doi10.1063/5.0048699
dc.identifier.urihttp://hdl.handle.net/1993/36077
dc.language.isoengen_US
dc.publisherJournal of Chemical Physicsen_US
dc.rightsopen accessen_US
dc.subjectmicrowave spectroscopyen_US
dc.subjectquantum chemistry calculationsen_US
dc.subjectpotential energy surfaceen_US
dc.subjectconformersen_US
dc.subjectconformational preferencesen_US
dc.titleConformational preferences of diallylamine: A rotational spectroscopic and theoretical studyen_US
dc.typePreprinten_US
local.author.affiliationFaculty of Scienceen_US
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