Advances in theoretical and physical aspects of spin-spin coupling constants

Contreras, Rubén H.; Peralta, Juan E.; Giribet, C. G.; Azúa, Martín C. Ruiz de; Facelli, Julio C.

doi:10.1016/s0066-4103(00)41009-4

Cited by 128 publications

(138 citation statements)

References 621 publications

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“…A set of 1s Gaussian AOs with a comparable range of innermost density maxima would afford exponents up to about 10 11 . In the benchmarks for the Hg atom and Hg 2 2 + , the finite-nucleus hyperfine integrals were reasonably well converged with basis TZ2P3 (highest STO exponent around 3 to 4 10 4 ). Production runs for the larger complexes were therefore performed with this basis set for the heavy atoms.…”

Section: Computational Detailsmentioning

confidence: 80%

“…Interestingly, for a pristine Hg 2 2 + ion, computations indicated that JA C H T U N G T R E N N U N G (HgÀHg) may reach almost one MHz [48] (computations have demonstrated the lack of thermodynamic stability of the Hg 2 2 + ion in the gas phase while the application of a continuum solvation model stabilizes the ion in solution [49] ). Thus, this section starts with some benchmark computations for the [HgÀHg] 2 + ion.…”

Section: Ja C H T U N G T R E N N U N G (Hgàhg) Of 284 Khz (mentioning

confidence: 99%

“…The conversion factor to J-coupling is 0.3941 kHz per 10 22 J T À2 based on a magnetogyric ratio of 4.846 10 7 rad s À1 T À1 for the 199 Hg nucleus. The results computed for Hg 2 2 + with different basis set and functionals are collected in Table 2. The FC term completely dominates the coupling in this ion.…”

Section: Ja C H T U N G T R E N N U N G (Hgàhg) Of 284 Khz (mentioning

confidence: 99%

“…Because of the importance of NMR in chemistry and related disciplines, much effort has been devoted to developments of theoretical tools to compute J-coupling and chemical shifts from first-principles theory. [1][2][3] For NMR parameters of heavy elements, a relativistic theory is needed. [4,5] Moreover, NMR parameters are sensitive to electron correlation.…”

Section: Introductionmentioning

confidence: 99%

“…For a subset of the systems studied, viz. the Hg atom, Hg 2 2 + , and TlÀX where X = Br, I, the basis set convergence of the hyperfine integrals and the coupling constants was monitored. For the Hg atom, numerical and basis set calculations of the electron density and the 1s and 6s orbital hyperfine integrals are directly compared.…”

Section: Introductionmentioning

confidence: 99%

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Magnitude of Finite‐Nucleus‐Size Effects in Relativistic Density Functional Computations of Indirect NMR Nuclear Spin–Spin Coupling Constants

Autschbach

2009

ChemPhysChem

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A spherical Gaussian nuclear charge distribution model has been implemented for spin-free (scalar) and two-component (spin-orbit) relativistic density functional calculations of indirect NMR nuclear spin-spin coupling (J-coupling) constants. The finite nuclear volume effects on the hyperfine integrals are quite pronounced and as a consequence they noticeably alter coupling constants involving heavy NMR nuclei such as W, Pt, Hg, Tl, and Pb. Typically, the isotropic J-couplings are reduced in magnitude by about 10 to 15 % for couplings between one of the heaviest NMR nuclei and a light atomic ligand, and even more so for couplings between two heavy atoms. For a subset of the systems studied, viz. the Hg atom, Hg(2) (2+), and Tl--X where X=Br, I, the basis set convergence of the hyperfine integrals and the coupling constants was monitored. For the Hg atom, numerical and basis set calculations of the electron density and the 1s and 6s orbital hyperfine integrals are directly compared. The coupling anisotropies of TlBr and TlI increase by about 2 % due to finite-nucleus effects.

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Section: Computational Detailsmentioning

confidence: 80%

Section: Ja C H T U N G T R E N N U N G (Hgàhg) Of 284 Khz (mentioning

confidence: 99%

Section: Ja C H T U N G T R E N N U N G (Hgàhg) Of 284 Khz (mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Magnitude of Finite‐Nucleus‐Size Effects in Relativistic Density Functional Computations of Indirect NMR Nuclear Spin–Spin Coupling Constants

Autschbach

2009

ChemPhysChem

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NMR Scalar Couplings and Molecular Interactions

Barone

Peralta

Contreras

1998

Encyclopedia of Computational Chemistry

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In this work, a description is given of the possibilities that, at present, can be envisioned for using NMR scalar spin–spin couplings for studying molecular systems. Such possibilities are based both on the application of computational chemistry approaches to calculate them and on the using of modern experimental techniques to measure them. This article intends to be useful to scientists who are not familiar with the theoretical background of scalar couplings. The organization of this work proceeds as follows: First, a short description is given of the nucleus–electron magnetic interactions that originate these spectral parameters. Second, some comments on the current approaches to calculate them are quoted, and adequate references are given for readers interested in deepening their theoretical background. Third, the potential of scalar couplings to study inter‐ and intramolecular interactions is illustrated. This is accomplished by discussing how the Fermi contact contribution to ${}^{1}J_{\rm CH}$ as well as to several types of geminal scalar couplings is influenced by hyperconjugative interactions. A qualitative analysis is presented for geminal couplings involving nuclei of lone‐pair–bearing atoms in order to explain under which conditions their paramagnetic spin‐orbital contribution could be substantial. Two different examples are presented in which, for similar configurations of lone pairs, the roles played by such lone pairs in coupling transmission are quite different.

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Relativistic Calculations of Spin–Spin Coupling Constants of Heavy Nuclei

Autschbach

Ziegler

2004

Calculation of NMR and EPR Parameters

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Advances in theoretical and physical aspects of spin-spin coupling constants

Cited by 128 publications

References 621 publications

Magnitude of Finite‐Nucleus‐Size Effects in Relativistic Density Functional Computations of Indirect NMR Nuclear Spin–Spin Coupling Constants

Magnitude of Finite‐Nucleus‐Size Effects in Relativistic Density Functional Computations of Indirect NMR Nuclear Spin–Spin Coupling Constants

NMR Scalar Couplings and Molecular Interactions

Relativistic Calculations of Spin–Spin Coupling Constants of Heavy Nuclei

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