Relativistic Spin-Orbit Heavy Atom on the Light Atom NMR
Chemical Shifts: General Trends Across the Periodic Table
Explained

J 2018

Relativistic Spin-Orbit Heavy Atom on the Light Atom NMR Chemical Shifts: General Trends Across the Periodic Table Explained

VÍCHA, Jan; Stanislav KOMOROVSKY; Michal REPISKY; Radek MAREK; Michal STRAKA et. al.

Základní údaje

Originální název

Relativistic Spin-Orbit Heavy Atom on the Light Atom NMR Chemical Shifts: General Trends Across the Periodic Table Explained

Autoři

VÍCHA, Jan (203 Česká republika); Stanislav KOMOROVSKY (703 Slovensko); Michal REPISKY (703 Slovensko); Radek MAREK (203 Česká republika, garant, domácí) a Michal STRAKA (203 Česká republika)

Vydání

Journal of Chemical Theory and Computation, American Chemical Society, 2018, 1549-9618

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10400 1.4 Chemical sciences

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

DOI: 10.1021/acs.jctc.8b00144

Impakt faktor

Impact factor: 5.313

Kód RIV

RIV/00216224:14740/18:00100905

Organizační jednotka

Středoevropský technologický institut

DOI

http://dx.doi.org/10.1021/acs.jctc.8b00144

UT WoS

000435416200019

EID Scopus

2-s2.0-85046296572

Klíčová slova anglicky

nuclear magnetic resonance;NMR;chemical shift;spin-orbit coupling;shielding;perturbation theory

Štítky

rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 13. 3. 2019 16:46, Mgr. Pavla Foltynová, Ph.D.

Anotace

V originále

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 have been missing. By analyzing 1H NMR chemical shifts of the 6th-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, 6p0 HA hydrides. This general and intuitive concept explains periodic trends in the 1H NMR chemical shifts along the 6th-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 non-hydride LAs. The decades-old question why compounds with occupied frontier pi molecular orbitals (MOs) cause SO-HALA shielding at the LA nuclei, while the frontier sigma 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, which 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 magnetic field. Using an analogy between 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.

Návaznosti

GA16-05961S, projekt VaV

Název: Pokročilé nosiče platinových léčiv

Investor: Grantová agentura ČR, Pokročilé nosiče platinových léčiv

LM2015085, projekt VaV

Název: CERIT Scientific Cloud (Akronym: CERIT-SC)

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, CERIT Scientific Cloud

LQ1601, projekt VaV

Název: CEITEC 2020 (Akronym: CEITEC2020)

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, CEITEC 2020

8X17009, projekt VaV

Název: Relativistické efekty v molekulárních materiálech založených na komplexech zlata: katalytická aktivita, přenos protonu a NMR vlastnosti (Akronym: GOLDCAT)

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Relativistic Effects in Molecular Materials Based on Gold Complexes: Catalytic Activity, Proton Transfer, and NMR Properties

Přiložené soubory

JCTC18_14_3025.pdf

Požádat o autorskou verzi souboru

Citovat

VÍCHA, Jan; Stanislav KOMOROVSKY; Michal REPISKY; Radek MAREK a Michal STRAKA. Relativistic Spin-Orbit Heavy Atom on the Light Atom NMR Chemical Shifts: General Trends Across the Periodic Table Explained. Journal of Chemical Theory and Computation. American Chemical Society, 2018, roč. 14, č. 6, s. 3025-3039. ISSN 1549-9618. Dostupné z: https://dx.doi.org/10.1021/acs.jctc.8b00144.

@article{1414596,
   author = {Vícha, Jan and Komorovsky, Stanislav and Repisky, Michal and Marek, Radek and Straka, Michal},
   article_number = {6},
   doi = {http://dx.doi.org/10.1021/acs.jctc.8b00144},
   keywords = {nuclear magnetic resonance;NMR;chemical shift;spin-orbit coupling;shielding;perturbation theory},
   language = {eng},
   issn = {1549-9618},
   journal = {Journal of Chemical Theory and Computation},
   title = {Relativistic Spin-Orbit Heavy Atom on the Light Atom NMR Chemical Shifts: General Trends Across the Periodic Table Explained},
   url = {http://dx.doi.org/10.1021/acs.jctc.8b00144},
   volume = {14},
   year = {2018}
}

TY  - JOUR
ID  - 1414596
AU  - Vícha, Jan - Komorovsky, Stanislav - Repisky, Michal - Marek, Radek - Straka, Michal
PY  - 2018
TI  - Relativistic Spin-Orbit Heavy Atom on the Light Atom NMR Chemical Shifts: General Trends Across the Periodic Table Explained
JF  - Journal of Chemical Theory and Computation
VL  - 14
IS  - 6
SP  - 3025-3039
EP  - 3025-3039
PB  - American Chemical Society
SN  - 15499618
KW  - nuclear magnetic resonance;NMR;chemical shift;spin-orbit coupling;shielding;perturbation theory
UR  - http://dx.doi.org/10.1021/acs.jctc.8b00144
L2  - http://dx.doi.org/10.1021/acs.jctc.8b00144
N2  - 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 have been missing. By analyzing 1H NMR chemical shifts of the 6th-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, 6p0 HA hydrides. This general and intuitive concept explains periodic trends in the 1H NMR chemical shifts along the 6th-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 non-hydride LAs. The decades-old question why compounds with occupied frontier pi molecular orbitals (MOs) cause SO-HALA shielding at the LA nuclei, while the frontier sigma 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, which 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 magnetic field. Using an analogy between 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.
ER  -

VÍCHA, Jan; Stanislav KOMOROVSKY; Michal REPISKY; Radek MAREK a Michal STRAKA. Relativistic Spin-Orbit Heavy Atom on the Light Atom NMR Chemical Shifts: General Trends Across the Periodic Table Explained. \textit{Journal of Chemical Theory and Computation}. American Chemical Society, 2018, roč.~14, č.~6, s.~3025-3039. ISSN~1549-9618. Dostupné z: https://dx.doi.org/10.1021/acs.jctc.8b00144.

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