First principles static and dynamic calculations for the transition metal hydride series MH4L3 (M = Fe, Ru and Os; L = NH3, PH3 and PF3)

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dc.contributor.authorSieffert, Nicolas
dc.contributor.authorKendrick, Thomas
dc.contributor.authorTiana, Davide
dc.contributor.authorMorrison, Carole A.
dc.contributor.funderSeventh Framework Programmeen
dc.contributor.funderEngineering and Physical Sciences Research Councilen
dc.contributor.funderGrand Équipement National De Calcul Intensifen
dc.contributor.funderUniversité Grenoble Alpesen
dc.contributor.funderCentre National de la Recherche Scientifiqueen
dc.date.accessioned2018-07-05T09:16:30Z
dc.date.available2018-07-05T09:16:30Z
dc.date.issued2015-01-20
dc.date.updated2018-07-03T11:23:42Z
dc.description.abstractWe present a first principles static and dynamical study of the transition metal hydride series MH4L3 (M = Fe, Ru and Os; L = NH3, PH3 and PF3), with a view to arriving at an understanding of how the variation in the electronic properties of the metal sites and ligands can influence the dynamics of the resulting complexes. A broad range of behaviour was observed, encompassing stable classical minima (M = Os, L = NH3 and M = Ru, L = PH3) to stable eta(2)-H-2 non-classical minima (M = Fe, L = PF3 and M = Ru, L = PH3 or PF3), with the other structures exhibiting dynamical behaviour that spontaneously converted between the classical and non-classical states during the molecular dynamics simulations. The importance of a small L-axial-M-L-axial angle in stabilising the non-classical state is highlighted, as is a short eta(2)-H-2 center dot center dot center dot H-cis distance in non-classical complexes that spontaneously convert to the classical form. We also investigated the changes in the electronic structure of the complex FeH4(PH3)(3) during a eta(2)-H-2 bond breaking/bond making reaction and observed direct evidence of the 'cis effect', whereby a neighbouring hydride ligand acts to stabilise the intermediate classical state.en
dc.description.sponsorshipEngineering and Physical Sciences Research Council (use of the facilities of HECToR, the UK’s national high-performance computing service, which is provided by UoE HPCx Ltd at the University of Edinburgh, Cray Inc and NAG Ltd, and funded by the Office of Science and Technology through EPSRC’s High End Computing Programme); Grand Équipement National De Calcul Intensif (HPC resources of IDRIS under the allocation 2013-i2011086670 made by GENCI); L'Institut de Chimie Moléculaire de Grenoble (ICMG FR 2607)en
dc.description.statusPeer revieweden
dc.description.versionPublished Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationSieffert, N., Kendrick, T., Tiana, D. and Morrison, C. A. (2015) 'First principles static and dynamic calculations for the transition metal hydride series MH4L3 (M = Fe, Ru and Os; L = NH3, PH3 and PF3)', Dalton Transactions, 44(9), pp. 4259-4270. doi: 10.1039/c4dt02475cen
dc.identifier.doi10.1039/c4dt02475c
dc.identifier.endpage4270en
dc.identifier.issn1477-9226
dc.identifier.journaltitleDalton Transactionsen
dc.identifier.startpage4259en
dc.identifier.urihttps://hdl.handle.net/10468/6413
dc.identifier.volume44en
dc.language.isoenen
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.projectinfo:eu-repo/grantAgreement/EC/FP7::SP4::INFRA/228398/EU/Pan-European Research infrastructure on High Performance Computing for 21st century Science/HPC-EUROPA2en
dc.rights© The Royal Society of Chemistry 2015. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.en
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/en
dc.subjectInteracting quantum atomsen
dc.subjectComplexesen
dc.subjectHydrogenen
dc.subjectPseudopotentialsen
dc.subjectDistributionsen
dc.subjectLocalizationen
dc.subjectEquilibriumen
dc.subjectReactivityen
dc.subjectDihydrogenen
dc.subjectMoleculesen
dc.subjectHydridesen
dc.subjectCalculationsen
dc.subjectComplexationen
dc.subjectElectronic propertiesen
dc.subjectElectronic structureen
dc.subjectIron compoundsen
dc.subjectLigandsen
dc.subjectMolecular dynamicsen
dc.subjectOsmiumen
dc.subjectReaction intermediatesen
dc.subjectReaction kineticsen
dc.subjectRutheniumen
dc.subjectTransition metal compoundsen
dc.subjectTransition metalsen
dc.titleFirst principles static and dynamic calculations for the transition metal hydride series MH4L3 (M = Fe, Ru and Os; L = NH3, PH3 and PF3)en
dc.typeArticle (peer-reviewed)en
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