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Structure, solvent, and relativistic effects on the NMR chemical shifts in square-planar transition-metal complexes: assessment of DFT approaches

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dc.title Structure, solvent, and relativistic effects on the NMR chemical shifts in square-planar transition-metal complexes: assessment of DFT approaches en
dc.contributor.author Vícha, Jan
dc.contributor.author Novotný, Jan
dc.contributor.author Straka, Michal
dc.contributor.author Repisky, Michal
dc.contributor.author Ruud, Kenneth
dc.contributor.author Komorovsky, Stanislav
dc.contributor.author Marek, Radek
dc.relation.ispartof Physical Chemistry Chemical Physics
dc.identifier.issn 1463-9076 Scopus Sources, Sherpa/RoMEO, JCR
dc.date.issued 2015
utb.relation.volume 17
utb.relation.issue 38
dc.citation.spage 24944
dc.citation.epage 24955
dc.type article
dc.language.iso en
dc.publisher Royal Society of Chemistry (RSC)
dc.identifier.doi 10.1039/c5cp04214c
dc.relation.uri http://pubs.rsc.org/en/Content/ArticleLanding/2015/CP/C5CP04214C#!divAbstract
dc.description.abstract The role of various factors (structure, solvent, and relativistic treatment) was evaluated for square-planar 4d and 5d transition-metal complexes. The DFT method for calculating the structures was calibrated using a cluster approach and compared to X-ray geometries, with the PBE0 functional (def2-TZVPP basis set) providing the best results, followed closely by the hybrid TPSSH and the MN12SX functionals. Calculations of the NMR chemical shifts using the two-component (2c, Zeroth-Order Regular Approximation as implemented in the ADF package) and four-component (4c, Dirac-Coulomb as implemented in the ReSpect code) relativistic approaches were performed to analyze and demonstrate the importance of solvent corrections (2c) as well as a proper treatment of relativistic effects (4c). The importance of increased exact-exchange admixture in the functional (here PBE0) for reproducing the experimental data using the current implementation of the 2c approach is partly rationalized as a compensation for the missing exchange-correlation response kernel. The kernel contribution was identified to be about 15-20% of the spin-orbit-induced NMR chemical shift, DdSO, which roughly corresponds to an increase in DdSO introduced by the artificially increased exact-exchange admixture in the functional. Finally, the role of individual effects (geometry, solvent, relativity) in the NMR chemical shift is discussed in selected complexes. Although a fully relativistic DFT approach is still awaiting the implementation of GIAOs for hybrid functionals and an implicit solvent model, it nevertheless provides reliable NMR chemical shift data at an affordable computational cost. It is expected to outperform the 2c approach, in particular for the calculation of NMR parameters in heavy-element compounds. en
utb.faculty University Institute
dc.identifier.uri http://hdl.handle.net/10563/1005695
utb.identifier.rivid RIV/70883521:28610/15:43873180!RIV16-MSM-28610___
utb.identifier.obdid 43873611
utb.identifier.scopus 2-s2.0-84942455846
utb.identifier.wok 000361697400043
utb.identifier.pubmed 26344822
utb.identifier.coden PPCPF
utb.source j-wok
dc.date.accessioned 2015-11-05T11:27:35Z
dc.date.available 2015-11-05T11:27:35Z
dc.description.sponsorship Czech Science Foundation [15-09381S, 14-03564S]; European Regional Development Fund [CZ.1.05/1.1.00/02.0068]; Research Council of Norway through a Centre of Excellence [179568, 214095, 177558]; Czech-Norway mobility grant from Norway Funds [NF-CZ07-MOP-3-245-2015]; program Center CERIT Scientific Cloud, part of the Operational Program Research and Development for Innovations [CZ.1.05/3.2.00/08.0144]
dc.rights Attribution-NonCommercial-NoDerivs 3.0 Unported
dc.rights.uri http://creativecommons.org/licenses/by-nc-nd/3.0/
dc.rights.access openAccess
utb.ou Centre of Polymer Systems
utb.contributor.internalauthor Vícha, Jan
utb.fulltext.affiliation Jan Vícha ‡,a,b, Jan Novotný ‡,a, Michal Straka a,c, Michal Repisky d, Kenneth Ruud d, Stanislav Komorovsky d*, Radek Marek *a,e a CEITEC – Central European Institute of Technology, Masaryk University, Kamenice 5/A4, CZ-62500 Brno, Czech Republic. E-mail: radek.marek@ceitec.muni.cz b Centre of Polymer Systems, University Institute, Tomas Bata University in Zlin, Trida T. Bati 5678, CZ-76001 Zlin, Czech Republic c Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo nám. 2, CZ-16610 Prague, Czech Republic d Centre for Theoretical and Computational Chemistry, Department of Chemistry, UiT – The Arctic University of Norway, N-9037 Tromsø, Norway. E-mail: stanislav.komorovsky@uit.no e Department of Chemistry, Faculty of Science, Masaryk University, Kamenice 5, CZ-62500 Brno, Czech Republic † Electronic supplementary information (ESI) available. Fig. S1: role of dispersion (empirical D3 correction) in cluster-based geometry optimizations; Fig. S2: the RMSDs (pm) for the interatomic distances according to the type of central metal; Fig. S3: the RMSDs (pm) for the interatomic distances according to the type of the light spectator atom; Fig. S4: comparison of total RMSDs (in pm) for interatomic distances calculated in vacuo and in cluster; Fig. S5: the 4c mDKS NMR chemical shifts with and without empirical ‘‘CGO corrections’’. Table S1: the Dd (ppm), in vacuo; Table S2: the Dd (ppm), COSMO; Table S3: the DdXC kernel values (ppm). See DOI: 10.1039/c5cp04214c ‡ These two authors contributed equally.
utb.fulltext.dates Received 18th July 2015 Accepted 24th August 2015
utb.fulltext.faculty University Institute
utb.fulltext.ou Centre of Polymer Systems
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