Full finite perturbation calculations of NMR screening constants and higher order effects

Boucekkine, Abdou; Boucekkine-Yaker, G.; Achour, M. Nait; Berthier, G.

doi:10.1016/0166-1280(88)80421-4

Cited by 10 publications

(2 citation statements)

References 7 publications

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“…Ramsey was the first to point out the possible magnetic-field dependence of the nuclear shieldings, and an estimate as well as an experimental determination were presented by Bendall and co-workers. , Raynes and Stevens estimated a change of 0.001 Hz in the spin−spin coupling in fields with a strength of 14 T, which they believe may be observable in experiments . The only ab initio calculation has been done for the nuclear shielding of H - …”

Section: Nmr-related Propertiesmentioning

confidence: 99%

Ab Initio Methods for the Calculation of NMR Shielding and Indirect Spin−Spin Coupling Constants

1998

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Section: Nmr-related Propertiesmentioning

confidence: 99%

Ab Initio Methods for the Calculation of NMR Shielding and Indirect Spin−Spin Coupling Constants

1998

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“…Magnetic fielddependent nuclear spin-spin coupling was discussed by Raynes and Stevens via fourth-order perturbation theory. 34 A few semiempirical 35,36 and ab initio calculations 37 have been carried out. Theoretical aspects of the magnetic-field dependence of quadrupole splitting in 131 Xe were considered by Vaara and Pykko ¨, who presented accurate numerical predictions 38 in good agreement with corresponding experi-mental values.…”

Section: Perturbation Theory Approach To Cubic Responsementioning

confidence: 99%

Can Induced Orbital Paramagnetism Be Controlled by Strong Magnetic Fields?

Pagola¹,

Ferraro²,

Lazzeretti³

2009

J. Chem. Theory Comput.

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Magnetic hypersusceptibilities and hypershielding at the nuclei of BH, CH(+), C4H4, and C8H8 molecules in the presence of an external spatially uniform, time-independent magnetic field have been investigated accounting for cubic response contributions via Rayleigh-Schrödinger perturbation theory. Numerical estimates have been obtained at the coupled Hartree-Fock and density-functional levels of theory within the conventional common-origin approach, using extended gaugeless basis sets. The fundamental role of electron correlation effects was assessed. Critical values of the applied magnetic field at which transition from paramagnetic to diamagnetic behavior would occur were estimated. It is shown that perturbative methods may successfully be employed to estimate the interaction energy for big cyclic molecules.

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Magnetic field‐dependent nuclear spin–spin coupling

Raynes

Stevens

1992

Magnetic Reson in Chemistry

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As the magnetic fields used in NMR spectrometers become greater, it is expected that a field dependence of nuclear spin-spin coupling will be observed. A part of this, which would be independent of temperature, is due to the contributions of higher terms in the Hamiltonian of the molecule in the external magnetic field and the two nuclear spin operators. Perturbation theory at second, third and fourth order is used to extract the general features of these higher order terms. Contributions are due (a) to diamagnetic and paramagnetic terms of each of the four familiar parts of the spin c o u p l i e Fermi contact, spidipolar, and orbital paramagnetic and orbital diamagnetic, and (b) to cross-terms determined by operators for the diamagnetic and paramagnetic shielding at the two coupled nuclei. Explicit expressions are presented for the more important contributions. It is estimated for strongly magnetic nuclei in large molecules that the coupling varies as 0.5 x lo-' Bz Hz, so that a field of about 14 T should produce a change in the coupling of 0.001 Hz. These are, respectively, the field used in high-field NMR spectrometers and the upper limit of precision in the measurement of spin-spin coupling constants at the present time.

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Full finite perturbation calculations of NMR screening constants and higher order effects

Cited by 10 publications

References 7 publications

Ab Initio Methods for the Calculation of NMR Shielding and Indirect Spin−Spin Coupling Constants

Ab Initio Methods for the Calculation of NMR Shielding and Indirect Spin−Spin Coupling Constants

Can Induced Orbital Paramagnetism Be Controlled by Strong Magnetic Fields?

Magnetic field‐dependent nuclear spin–spin coupling

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