Quadratic Spin–Orbit Mechanism of the Electronic g-Tensor

J 2023

Quadratic Spin–Orbit Mechanism of the Electronic g-Tensor

PIKULOVÁ, Petra; Debora MISENKOVA; Radek MAREK; Stanislav KOMOROVSKY; Jan NOVOTNÝ et al.

Základní údaje

Originální název

Quadratic Spin–Orbit Mechanism of the Electronic g-Tensor

Autoři

PIKULOVÁ, Petra; Debora MISENKOVA; Radek MAREK ; Stanislav KOMOROVSKY a Jan NOVOTNÝ

Vydání

Journal of Chemical Theory and Computation, American Chemical Society, 2023, 1549-9618

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10403 Physical chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Odkazy

DOI: 10.1021/acs.jctc.2c01213

Impakt faktor

Impact factor: 5.700

Kód RIV

RIV/00216224:14740/23:00130431

Organizační jednotka

Středoevropský technologický institut

DOI

https://doi.org/10.1021/acs.jctc.2c01213

UT WoS

000962854500001

EID Scopus

2-s2.0-85149762543

Klíčová slova česky

Electronová paramagntická rezonance; g tenzor; spin-orbitální interakce; teorie MO

Klíčová slova anglicky

Electron paramagnetic resonance; g tensor; spin-orbit coupling; MO theory

Štítky

14313010, rivok

Příznaky

Mezinárodní význam, Recenzováno

Změněno: 7. 3. 2024 10:12, Mgr. Eva Dubská

Anotace

V originále

Understanding how the electronic g-tensor is linked to the electronic structure is desirable for the correct interpretation of electron paramagnetic resonance spectra. For heavy-element compounds with large spin–orbit (SO) effects, this is still not completely clear. We report our investigation of quadratic SO contributions to the g-shift in heavy transition metal complexes. We implemented third-order perturbation theory in order to analyze the contributions arising from frontier molecular spin orbitals (MSOs). We show that the dominant quadratic SO term─spin-Zeeman (SO2/SZ)─generally makes a negative contribution to the g-shift, irrespective of the particular electronic configuration or molecular symmetry. We further analyze how the SO2/SZ contribution adds to or subtracts from the linear orbital-Zeeman (SO/OZ) contribution to the individual principal components of the g-tensor. Our study suggests that the SO2/SZ mechanism decreases the anisotropy of the g-tensor in early transition metal complexes and increases it in late transition metal complexes. Finally, we apply MSO analysis to the investigation of g-tensor trends in a set of closely related Ir and Rh pincer complexes and evaluate the influence of different chemical factors (the nuclear charge of the central atom and the terminal ligand) on the magnitudes of the g-shifts. We expect our conclusions to aid the understanding of spectra in magnetic resonance investigations of heavy transition metal compounds.

Návaznosti

GA21-06991S, projekt VaV

Název: Relativistické efekty v paramagnetické NMR spektroskopii (Akronym: RELMAG)

Investor: Grantová agentura ČR, Relativistické efekty v paramagnetické NMR spektroskopii

MUNI/C/0107/2022, interní kód MU

Název: Výpočty NMR a EPR parametrů pomocí nástrojů relativistické kvantové chemie

Investor: Masarykova univerzita, Výpočty NMR a EPR parametrů pomocí nástrojů relativistické kvantové chemie, Podpora vynikajících diplomových prací

90140, velká výzkumná infrastruktura

Název: e-INFRA CZ

Přiložené soubory

JCTC23_19_1765_acs.jctc.2c01213.pdf

Požádat o autorskou verzi souboru

Citovat

PIKULOVÁ, Petra; Debora MISENKOVA; Radek MAREK; Stanislav KOMOROVSKY a Jan NOVOTNÝ. Quadratic Spin–Orbit Mechanism of the Electronic g-Tensor. Journal of Chemical Theory and Computation. American Chemical Society, 2023, roč. 19, č. 6, s. 1765-1776. ISSN 1549-9618. Dostupné z: https://doi.org/10.1021/acs.jctc.2c01213.

@article{2266460,
   author = {Pikulová, Petra and Misenkova, Debora and Marek, Radek and Komorovsky, Stanislav and Novotný, Jan},
   article_number = {6},
   doi = {https://doi.org/10.1021/acs.jctc.2c01213},
   keywords = {Electron paramagnetic resonance; g tensor; spin-orbit coupling; MO theory},
   language = {eng},
   issn = {1549-9618},
   journal = {Journal of Chemical Theory and Computation},
   title = {Quadratic Spin–Orbit Mechanism of the Electronic g-Tensor},
   url = {http://dx.doi.org/10.1021/acs.jctc.2c01213},
   volume = {19},
   year = {2023}
}

TY  - JOUR
ID  - 2266460
AU  - Pikulová, Petra - Misenkova, Debora - Marek, Radek - Komorovsky, Stanislav - Novotný, Jan
PY  - 2023
TI  - Quadratic Spin–Orbit Mechanism of the Electronic g-Tensor
JF  - Journal of Chemical Theory and Computation
VL  - 19
IS  - 6
SP  - 1765-1776
EP  - 1765-1776
PB  - American Chemical Society
SN  - 15499618
KW  - Electron paramagnetic resonance
KW  - g tensor
KW  - spin-orbit coupling
KW  - MO theory
UR  - http://dx.doi.org/10.1021/acs.jctc.2c01213
N2  - Understanding how the electronic g-tensor is linked to the electronic structure is desirable for the correct interpretation of electron paramagnetic resonance spectra. For heavy-element compounds with large spin–orbit (SO) effects, this is still not completely clear. We report our investigation of quadratic SO contributions to the g-shift in heavy transition metal complexes. We implemented third-order perturbation theory in order to analyze the contributions arising from frontier molecular spin orbitals (MSOs). We show that the dominant quadratic SO term─spin-Zeeman (SO2/SZ)─generally makes a negative contribution to the g-shift, irrespective of the particular electronic configuration or molecular symmetry. We further analyze how the SO2/SZ contribution adds to or subtracts from the linear orbital-Zeeman (SO/OZ) contribution to the individual principal components of the g-tensor. Our study suggests that the SO2/SZ mechanism decreases the anisotropy of the g-tensor in early transition metal complexes and increases it in late transition metal complexes. Finally, we apply MSO analysis to the investigation of g-tensor trends in a set of closely related Ir and Rh pincer complexes and evaluate the influence of different chemical factors (the nuclear charge of the central atom and the terminal ligand) on the magnitudes of the g-shifts. We expect our conclusions to aid the understanding of spectra in magnetic resonance investigations of heavy transition metal compounds.
ER  -

PIKULOVÁ, Petra; Debora MISENKOVA; Radek MAREK; Stanislav KOMOROVSKY a Jan NOVOTNÝ. Quadratic Spin–Orbit Mechanism of the Electronic g-Tensor. \textit{Journal of Chemical Theory and Computation}. American Chemical Society, 2023, roč.~19, č.~6, s.~1765-1776. ISSN~1549-9618. Dostupné z: https://doi.org/10.1021/acs.jctc.2c01213.

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