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Relativistic spin-orbit heavy atom on the light atom NMR chemical shifts: General trends across the periodic table explained

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dc.title Relativistic spin-orbit heavy atom on the light atom NMR chemical shifts: General trends across the periodic table explained en
dc.contributor.author Vícha, Jan
dc.contributor.author Komorovsky, Stanislav
dc.contributor.author Repisky, Michal
dc.contributor.author Marek, Radek
dc.contributor.author Straka, Michal
dc.relation.ispartof Journal of Chemical Theory and Computation
dc.identifier.issn 1549-9618 Scopus Sources, Sherpa/RoMEO, JCR
dc.date.issued 2018
utb.relation.volume 14
utb.relation.issue 6
dc.citation.spage 3025
dc.citation.epage 3039
dc.type article
dc.language.iso en
dc.publisher American Chemical Society
dc.identifier.doi 10.1021/acs.jctc.8b00144
dc.relation.uri https://pubs.acs.org/doi/abs/10.1021/acs.jctc.8b00144
dc.description.abstract The importance of relativistic effects on the NMR parameters in heavy-atom (HA) compounds, particularly the SO-HALA (Spin-Orbit Heavy Atom on the Light Atom) effect on NMR chemical shifts, has been known for about 40 years. Yet, a general correlation between the electronic structure and SO-HALA effect has been missing. By analyzing 1H NMR chemical shifts of the sixth-period hydrides (Cs-At), we discovered general electronic-structure principles and mechanisms that dictate the size and sign of the SO-HALA NMR chemical shifts. In brief, partially occupied HA valence shells induce relativistic shielding at the light atom (LA) nuclei, while empty HA valence shells induce relativistic deshielding. In particular, the LA nucleus is relativistically shielded in 5d2-5d8 and 6p4 HA hydrides and deshielded in 4f0, 5d0, 6s0, and 6p0 HA hydrides. This general and intuitive concept explains periodic trends in the 1H NMR chemical shifts along the sixth-period hydrides (Cs-At) studied in this work. We present substantial evidence that the introduced principles have a general validity across the periodic table and can be extended to nonhydride LAs. The decades-old question of why compounds with occupied frontier π molecular orbitals (MOs) cause SO-HALA shielding at the LA nuclei, while the frontier σ MOs cause deshielding is answered. We further derive connection between the SO-HALA NMR chemical shifts and Spin-Orbit-induced Electron Deformation Density (SO-EDD), a property that can be obtained easily from differential electron densities and can be represented graphically. SO-EDD provides an intuitive understanding of the SO-HALA effect in terms of the depletion/concentration of the electron density at LA nuclei caused by spin-orbit coupling due to HA in the presence of a magnetic field. Using an analogy between the SO-EDD concept and arguments from classic NMR theory, the complex question of the SO-HALA NMR chemical shifts becomes easily understandable for a wide chemical audience. Copyright © 2018 American Chemical Society. en
utb.faculty University Institute
dc.identifier.uri http://hdl.handle.net/10563/1008056
utb.identifier.obdid 43878237
utb.identifier.scopus 2-s2.0-85046296572
utb.identifier.wok 000435416200019
utb.identifier.pubmed 29676906
utb.identifier.coden JCTCC
utb.source j-scopus
dc.date.accessioned 2018-07-27T08:47:42Z
dc.date.available 2018-07-27T08:47:42Z
dc.description.sponsorship DS-2016-0009; APVV-15-0726; 2/0116/17; EGU, European Geosciences Union; 8X17009; LM2015042; 1563/03/02, AV ČR, Akademie Věd České Republiky; RVO-61388963, AV ČR, Akademie Věd České Republiky; SAV, Slovenská Akadémia Vied; LQ1601; LO1504; 16-05961S, GACR, Grantová Agentura České Republiky; LM2015085
dc.description.sponsorship Czech Science Foundation [16-05961S]; Ministry of Education, Youth and Sports of the Czech Republic under the National Sustainability Program I [LO1504]; Ministry of Education, Youth and Sports of the Czech Republic under the National Sustainability Program II [LQ1601]; Multilateral Scientific and Technological Cooperation Project in the Danube Region [8X17009]; Czech Academy of Sciences [RVO-61388963]; SASPRO Program - European Union [1563/03/02]; Slovak Academy of Sciences; Slovak Grant Agency VEGA [2/0116/17, APVV-15-0726, DS-2016-0009]; Slovak Grant Agency APVV [2/0116/17, APVV-15-0726, DS-2016-0009]; CESNET [LM2015042]; CERIT Scientific Clouds [LM2015085]
utb.ou Centre of Polymer Systems
utb.contributor.internalauthor Vícha, Jan
utb.scopus.affiliation Center of Polymer Systems, University Institute, Tomas Bata University in Zlín, Třída T. Bati, 5678, Zlín, Czech Republic; Institute of Inorganic Chemistry, Slovak Academy of Science, Dúbravská cesta 9, Bratislava, Slovakia; Center for Theoretical and Computational Chemistry, Department of Chemistry, UiT - the Arctic University of Norway, Tromsø, Norway; CEITEC - Central European Institute of Technology, Masaryk University, Kamenice 5/A4, Brno, Czech Republic; Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences, Flemingovo nám. 2, Prague, Czech Republic
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