NMR Spin–Spin Coupling Constants Derived from
Relativistic Four-Component DFT TheoryAnalysis and Visualization
Posted on 2020-06-12 - 15:05
An
unambiguous assignment of coupling pathways plays an important
role in the description and rationalization of NMR indirect spin–spin
coupling constants (SSCCs). Unfortunately, the SSCC analysis and visualization
tools currently available to quantum chemists are restricted to nonrelativistic
theory. Here, we present the theoretical foundation for novel relativistic
SSCC visualization techniques based on analysis of the SSCC densities
and the first-order current densities induced by the nuclear magnetic
dipole moments. Details of the implementation of these techniques
in the ReSpect program package are discussed. Numerical assessments
are performed on through-space SSCCs, and we choose as our examples
the heavy-atom Se–Se, Se–Te, and Te–Te coupling
constants in three similar molecules for which experimental data are
available. SSCCs were calculated at the nonrelativistic, scalar relativistic,
and four-component relativistic density functional levels of theory.
Furthermore, with the aid of different visualization methods, we discuss
the interpretation of the relativistic effects, which are sizable
for Se–Se, very significant for Se–Te, and cannot be
neglected for Te–Te couplings. A substantial improvement of
the theoretical SSCC values is obtained by also considering the molecular
properties of a second conformation.
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Komorovsky, Stanislav; Jakubowska, Katarzyna; Świder, Paweł; Repisky, Michal; Jaszuński, Michał (2020). NMR Spin–Spin Coupling Constants Derived from
Relativistic Four-Component DFT TheoryAnalysis and Visualization. ACS Publications. Collection. https://doi.org/10.1021/acs.jpca.0c02807
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AUTHORS (5)
SK
Stanislav Komorovsky
KJ
Katarzyna Jakubowska
PS
Paweł Świder
MR
Michal Repisky
MJ
Michał Jaszuński