On the Utmost Importance of the Basis Set Choice for the Calculations of the Relativistic Corrections to NMR Shielding Constants

Rusakova, Irina L.; Rusakov, Yury Yu.

doi:10.3390/ijms24076231

Cited by 4 publications

(1 citation statement)

References 136 publications

(153 reference statements)

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“…The "10c limit scheme" is now a widely used approximation [24,25,93,94,[125][126][127][128][129]] that is applied to exclude the basis set inequivalence in passing from the four-component relativistic to the one-component nonrelativistic framework. The convergences of the selenium SSCCs with the increasing of the speed of light are shown in Figures S1 and S2 in the Supplementary Materials for the examples of 1 J(Se,H) in SeH 2 and 1 J(Se,C) in Se=C, respectively, calculated at the four-component DFT(SVWN5)//pecJ-2(uc) level.…”

Section: Testing New Basis Setsmentioning

confidence: 99%

New pecJ-n (n = 1, 2) Basis Sets for Selenium Atom Purposed for the Calculations of NMR Spin–Spin Coupling Constants Involving Selenium

Rusakov

Rusakova

2023

IJMS

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We present new compact pecJ-n (n = 1, 2) basis sets for the selenium atom developed for the quantum–chemical calculations of NMR spin–spin coupling constants (SSCCs) involving selenium nuclei. These basis sets were obtained at the second order polarization propagator approximation with coupled cluster singles and doubles amplitudes (SOPPA(CCSD)) level with the property-energy consistent (PEC) method, which was introduced in our previous papers. The existing SSCC-oriented selenium basis sets are rather large in size, while the PEC method gives more compact basis sets that are capable of providing accuracy comparable to that reached using the property-oriented basis sets of larger sizes generated with a standard even-tempered technique. This is due to the fact that the PEC method is very different in its essence from the even-tempered approaches. It generates new exponents through the total optimization of angular spaces of trial basis sets with respect to the property under consideration and the total molecular energy. New basis sets were tested on the coupled cluster singles and doubles (CCSD) calculations of SSCCs involving selenium in the representative series of molecules, taking into account relativistic, solvent, and vibrational corrections. The comparison with the experiment showed that the accuracy of the results obtained with the pecJ-2 basis set is almost the same as that provided by a significantly larger basis set, aug-cc-pVTZ-J, while that achieved with a very compact pecJ-1 basis set is only slightly inferior to the accuracy provided by the former.

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Section: Testing New Basis Setsmentioning

confidence: 99%

New pecJ-n (n = 1, 2) Basis Sets for Selenium Atom Purposed for the Calculations of NMR Spin–Spin Coupling Constants Involving Selenium

Rusakov

Rusakova

2023

IJMS

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The Scope of the Applicability of Non‐relativistic DFT Calculations of NMR Chemical Shifts in Pyridine‐Metal Complexes for Applied Applications

Shenderovich

2024

ChemPhysChem

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Heavy metals are toxic, but it is impossible to stop using them. Considering the variety of molecular systems in which they can be present, the multicomponent nature and disorder of the structure of such systems, one of the most effective methods for studying them is NMR spectroscopy. This determines the need to calculate NMR chemical shifts for expected model systems. For elements beyond the third row of the periodic table, corrections for relativistic effects are necessary when calculating NMR parameters. Such corrections may be necessary even for light atoms due to the shielding effect of a neighboring heavy atom. This work examines the extent to which non‐relativistic DFT calculations are able to reproduce experimental 15N and 113Cd NMR chemical shift tensors in pyridine‐metal coordination complexes. It is shown that while for the calculation of 15N NMR chemical shift tensors there is no real need to consider relativistic corrections, for 113Cd, on the contrary, none of the tested calculation methods could reproduce the experimentally obtained tensor to any extent correctly.

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Computational insights into the tailoring of photoelectric properties in graphene quantum dot-Ru(II) polypyridyl nanocomposites

Cui,

Wu,

Hou

et al. 2025

Computational Materials Science

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On the Utmost Importance of the Basis Set Choice for the Calculations of the Relativistic Corrections to NMR Shielding Constants

Cited by 4 publications

References 136 publications

New pecJ-n (n = 1, 2) Basis Sets for Selenium Atom Purposed for the Calculations of NMR Spin–Spin Coupling Constants Involving Selenium

New pecJ-n (n = 1, 2) Basis Sets for Selenium Atom Purposed for the Calculations of NMR Spin–Spin Coupling Constants Involving Selenium

The Scope of the Applicability of Non‐relativistic DFT Calculations of NMR Chemical Shifts in Pyridine‐Metal Complexes for Applied Applications

Computational insights into the tailoring of photoelectric properties in graphene quantum dot-Ru(II) polypyridyl nanocomposites

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