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.author Sieffert, Nicolas
dc.contributor.author Kendrick, Thomas
dc.contributor.author Tiana, Davide
dc.contributor.author Morrison, Carole A.
dc.date.accessioned 2018-07-05T09:16:30Z
dc.date.available 2018-07-05T09:16:30Z
dc.date.issued 2015-01-20
dc.identifier.citation Sieffert, 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/c4dt02475c en
dc.identifier.volume 44 en
dc.identifier.startpage 4259 en
dc.identifier.endpage 4270 en
dc.identifier.issn 1477-9226
dc.identifier.uri http://hdl.handle.net/10468/6413
dc.identifier.doi 10.1039/c4dt02475c
dc.description.abstract We 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.sponsorship Engineering 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.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher Royal Society of Chemistry (RSC) en
dc.rights © The Royal Society of Chemistry 2015. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. en
dc.rights.uri https://creativecommons.org/licenses/by/3.0/ en
dc.subject Interacting quantum atoms en
dc.subject Complexes en
dc.subject Hydrogen en
dc.subject Pseudopotentials en
dc.subject Distributions en
dc.subject Localization en
dc.subject Equilibrium en
dc.subject Reactivity en
dc.subject Dihydrogen en
dc.subject Molecules en
dc.subject Hydrides en
dc.subject Calculations en
dc.subject Complexation en
dc.subject Electronic properties en
dc.subject Electronic structure en
dc.subject Iron compounds en
dc.subject Ligands en
dc.subject Molecular dynamics en
dc.subject Osmium en
dc.subject Reaction intermediates en
dc.subject Reaction kinetics en
dc.subject Ruthenium en
dc.subject Transition metal compounds en
dc.subject Transition metals en
dc.title First principles static and dynamic calculations for the transition metal hydride series MH4L3 (M = Fe, Ru and Os; L = NH3, PH3 and PF3) en
dc.type Article (peer-reviewed) en
dc.internal.authorcontactother Davide Tiana, Chemistry, University College Cork, Cork, Ireland. +353-21-490-3000 Email: davide.tiana@ucc.ie en
dc.internal.availability Full text available en
dc.date.updated 2018-07-03T11:23:42Z
dc.description.version Published Version en
dc.internal.rssid 391816975
dc.internal.wokid WOS:000349993400042
dc.contributor.funder Seventh Framework Programme en
dc.contributor.funder Engineering and Physical Sciences Research Council en
dc.contributor.funder Grand Équipement National De Calcul Intensif en
dc.contributor.funder Université Grenoble Alpes en
dc.contributor.funder Centre National de la Recherche Scientifique en
dc.description.status Peer reviewed en
dc.identifier.journaltitle Dalton Transactions en
dc.internal.copyrightchecked Yes en
dc.internal.licenseacceptance Yes en
dc.internal.IRISemailaddress davide.tiana@ucc.ie en
dc.relation.project info:eu-repo/grantAgreement/EC/FP7::SP4::INFRA/228398/EU/Pan-European Research infrastructure on High Performance Computing for 21st century Science/HPC-EUROPA2 en


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© The Royal Society of Chemistry 2015. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Except where otherwise noted, this item's license is described as © The Royal Society of Chemistry 2015. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
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