Quadratic Spin–Orbit Mechanism of the Electronic g-Tensor
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14740%2F23%3A00130431" target="_blank" >RIV/00216224:14740/23:00130431 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1021/acs.jctc.2c01213" target="_blank" >http://dx.doi.org/10.1021/acs.jctc.2c01213</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.jctc.2c01213" target="_blank" >10.1021/acs.jctc.2c01213</a>
Alternative languages
Result language
angličtina
Original language name
Quadratic Spin–Orbit Mechanism of the Electronic g-Tensor
Original language description
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.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
<a href="/en/project/GA21-06991S" target="_blank" >GA21-06991S: Relativistic Effects in Paramagnetic NMR Spectroscopy</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Chemical Theory and Computation
ISSN
1549-9618
e-ISSN
1549-9626
Volume of the periodical
19
Issue of the periodical within the volume
6
Country of publishing house
US - UNITED STATES
Number of pages
12
Pages from-to
1765-1776
UT code for WoS article
000962854500001
EID of the result in the Scopus database
2-s2.0-85149762543