Link between Spin–Orbit Relativity and Magnetically Induced
Current Densities in Heavy-Atom Hydrides: trans-Ligand
Influence

J 2026

Link between Spin–Orbit Relativity and Magnetically Induced Current Densities in Heavy-Atom Hydrides: trans-Ligand Influence

BLASCO SANTANA, Daniel; Jan NOVOTNÝ; Jamer R. ASHER; Raphael J. F. BERGER; Stanislav KOMOROVSKY et al.

Základní údaje

Originální název

Link between Spin–Orbit Relativity and Magnetically Induced Current Densities in Heavy-Atom Hydrides: trans-Ligand Influence

Autoři

BLASCO SANTANA, Daniel ; Jan NOVOTNÝ; Jamer R. ASHER; Raphael J. F. BERGER; Stanislav KOMOROVSKY a Radek MAREK

Vydání

JACS Au, AMER CHEMICAL SOC, 2026, 2691-3704

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/jacsau.6c00346

Impakt faktor

Impact factor: 8.700 v roce 2024

Označené pro přenos do RIV

Ano

Organizační jednotka

Středoevropský technologický institut

DOI

https://doi.org/10.1021/jacsau.6c00346

UT WoS

001782421400001

Klíčová slova anglicky

electronic motion; spin-orbit coupling; magnetically induced current density; Dirac-Kohn-Sham level; trans-ligand influence; electronic structure; chemical shift; NMR; resonance spectra

Štítky

14313010

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 18. 7. 2026 09:38, prof. RNDr. Radek Marek, Ph.D.

Anotace

V originále

Interactions between individual atoms underpin the structure and behavior of matter. These interactions govern atomic positions and dynamics, as well as the organization of electrons─particularly in the frontier region. Because electrons lie at the core of chemical phenomena, numerous theoretical frameworks have been developed to rationalize the molecular structure and properties. Electronic motion within molecules and the resulting induced currents provide powerful probes of the molecular or supramolecular structure, building on and going beyond molecular orbital and valence bond theories. In particular, current density offers a spatially-resolved description of the electronic response to external perturbations, enabling direct analysis of electron delocalization and magnetic response in molecular systems. In this work, the effect of relativistic spin–orbit (SO) coupling on the strength and topology of the magnetically induced current density (MICD) is analyzed in depth for a series of model heavy-atom hydrides at the four-component Dirac-Kohn–Sham level. For the most simple molecules, TlH, HAt, and AuH, we demonstrate a connection between the SO effects on the molecular geometry, strength and topology of MICDs, and ligand 1H NMR shielding. For model HMX molecules, where M = AuI, HgII; X = F, Cl, Ph, CH3, H, SiH3, BH2, the hydride deshielding due to the slight elongation of the M–H bond upon increasing the trans-ligand influence (TLI) of X is shown to be marginal when compared to that originating from the electronic SO effect. In particular, the inclusion of SO effects gives rise to highly localized paratropic MICD vortices on the hydride position of those complexes bearing strong TLI ligands. Our results disprove the previously proposed governing role of the current around the metal atom (similar to the classical Buckingham-Stephens model for transition metal hydrides) associated with TLI-induced variations in the metal–hydrogen bond length in determining the characteristic ligand 1H NMR shifts.

Návaznosti

CZ.02.01.01/00/22_010/0013359, interní kód MU

Název: MSCAfellow8_MUNI

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, MSCAfellow8_MUNI, Priorita 1 - Výzkum a vývoj

GA24-10760S, projekt VaV

Název: Relativistické spin-orbitální efekty v molekulární struktuře a NMR spektroskopii

Investor: Grantová agentura ČR, Relativistické spin-orbitální efekty v molekulární struktuře a NMR spektroskopii

8X25011, projekt VaV

Název: Relativistické vlivy na magnetickou odezvu

Investor: Ministerstvo školství, mládeže a tělovýchovy ČR, Relativistické vlivy na magnetickou odezvu, Společné projekty - mobility

90254, velká výzkumná infrastruktura

Název: e-INFRA CZ II

Přiložené soubory

JACSAu26_6_3323.pdf

Požádat o autorskou verzi souboru

Citovat

BLASCO SANTANA, Daniel; Jan NOVOTNÝ; Jamer R. ASHER; Raphael J. F. BERGER; Stanislav KOMOROVSKY a Radek MAREK. Link between Spin–Orbit Relativity and Magnetically Induced Current Densities in Heavy-Atom Hydrides: trans-Ligand Influence. JACS Au. AMER CHEMICAL SOC, 2026, roč. 6, č. 6, s. 3323-3335. ISSN 2691-3704. Dostupné z: https://doi.org/10.1021/jacsau.6c00346.

@article{2576603,
   author = {Blasco Santana, Daniel and Novotný, Jan and Asher, Jamer R. and Berger, Raphael J. F. and Komorovsky, Stanislav and Marek, Radek},
   article_number = {6},
   doi = {https://doi.org/10.1021/jacsau.6c00346},
   keywords = {electronic motion; spin-orbit coupling; magnetically induced current density; Dirac-Kohn-Sham level; trans-ligand influence; electronic structure; chemical shift; NMR; resonance spectra},
   language = {eng},
   issn = {2691-3704},
   journal = {JACS Au},
   title = {Link between Spin–Orbit Relativity and Magnetically Induced Current Densities in Heavy-Atom Hydrides: trans-Ligand Influence},
   url = {https://doi.org/10.1021/jacsau.6c00346},
   volume = {6},
   year = {2026}
}

TY  - JOUR
ID  - 2576603
AU  - Blasco Santana, Daniel - Novotný, Jan - Asher, Jamer R. - Berger, Raphael J. F. - Komorovsky, Stanislav - Marek, Radek
PY  - 2026
TI  - Link between Spin–Orbit Relativity and Magnetically Induced Current Densities in Heavy-Atom Hydrides: trans-Ligand Influence
JF  - JACS Au
VL  - 6
IS  - 6
SP  - 3323-3335
EP  - 3323-3335
PB  - AMER CHEMICAL SOC
SN  - 26913704
KW  - electronic motion
KW  - spin-orbit coupling
KW  - magnetically induced current density
KW  - Dirac-Kohn-Sham level
KW  - trans-ligand influence
KW  - electronic structure
KW  - chemical shift
KW  - NMR
KW  - resonance spectra
UR  - https://doi.org/10.1021/jacsau.6c00346
N2  - Interactions between individual atoms underpin the structure and behavior of matter. These interactions govern atomic positions and dynamics, as well as the organization of electrons─particularly in the frontier region. Because electrons lie at the core of chemical phenomena, numerous theoretical frameworks have been developed to rationalize the molecular structure and properties. Electronic motion within molecules and the resulting induced currents provide powerful probes of the molecular or supramolecular structure, building on and going beyond molecular orbital and valence bond theories. In particular, current density offers a spatially-resolved description of the electronic response to external perturbations, enabling direct analysis of electron delocalization and magnetic response in molecular systems. In this work, the effect of relativistic spin–orbit (SO) coupling on the strength and topology of the magnetically induced current density (MICD) is analyzed in depth for a series of model heavy-atom hydrides at the four-component Dirac-Kohn–Sham level. For the most simple molecules, TlH, HAt, and AuH, we demonstrate a connection between the SO effects on the molecular geometry, strength and topology of MICDs, and ligand 1H NMR shielding. For model HMX molecules, where M = AuI, HgII; X = F, Cl, Ph, CH3, H, SiH3, BH2, the hydride deshielding due to the slight elongation of the M–H bond upon increasing the trans-ligand influence (TLI) of X is shown to be marginal when compared to that originating from the electronic SO effect. In particular, the inclusion of SO effects gives rise to highly localized paratropic MICD vortices on the hydride position of those complexes bearing strong TLI ligands. Our results disprove the previously proposed governing role of the current around the metal atom (similar to the classical Buckingham-Stephens model for transition metal hydrides) associated with TLI-induced variations in the metal–hydrogen bond length in determining the characteristic ligand 1H NMR shifts.
ER  -

BLASCO SANTANA, Daniel; Jan NOVOTNÝ; Jamer R. ASHER; Raphael J. F. BERGER; Stanislav KOMOROVSKY a Radek MAREK. Link between Spin–Orbit Relativity and Magnetically Induced Current Densities in Heavy-Atom Hydrides: trans-Ligand Influence. \textit{JACS Au}. AMER CHEMICAL SOC, 2026, roč.~6, č.~6, s.~3323-3335. ISSN~2691-3704. Dostupné z: https://doi.org/10.1021/jacsau.6c00346.

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