Full four-component relativistic calculations of NMR shielding and indirect spin-spin coupling tensors in hydrogen halides

Visscher, Lucas; Enevoldsen, Thomas; Saue, Trond; Jensen, Hans Jørgen Aagard; Oddershede, Jens

doi:10.1002/(sici)1096-987x(199909)20:12<1262::aid-jcc6>3.0.co;2-h

Cited by 190 publications

(150 citation statements)

References 34 publications

Supporting

Mentioning

138

Contrasting

Order By: Relevance

“…The nonequivalence of the relativistic theories of the NMS tensor and SR tensors anticipates the failure of Flygare's relation in the relativistic case. 22,24 However, as it is shown in the present series of compounds, in some cases, depending on the physical mechanism defining the relativistic effect, the relation may hold anyway.…”

Section: Discussion: Relativistic Corrections Lresc Expansion Anmentioning

confidence: 71%

“…39 Inserting these expressions in Eq. (22) and retaining terms bilinear in J (4) and A N it is found…”

Section: B Leading Relativistic Corrections Of the Spin-rotation Tenmentioning

confidence: 98%

“…The second order electronic contribution can be obtained by means of the relativistic 4-component linear response (lr) theory 22 at zero frequency, as the propagator…”

Section: A Relativistic 4-component Expression Of the Spin-rotation mentioning

confidence: 99%

“…[19][20][21] One interesting result which was anticipated long ago, is the fact that Flygare's relation would fail in the relativistic domain, due to differences in the 4-component operators that should describe the NMS and SR parameters. 22 In the early 2000, a relativistic expression of the closely related molecular g-tensor was analyzed. 23 Recently, a theoretical expression of the SR tensor at the equilibrium geometry of a molecular system in a 4-component framework was developed.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Theoretical study of the nuclear spin-molecular rotation coupling for relativistic electrons and non-relativistic nuclei. II. Quantitative results in HX (X=H,F,Cl,Br,I) compounds

Aucar

Gómez

Melo

et al. 2013

The Journal of Chemical Physics

View full text Add to dashboard Cite

In the present work, numerical results of the nuclear spin-rotation (SR) tensor in the series of compounds HX (X=H,F,Cl,Br,I) within relativistic 4-component expressions obtained by Aucar et al. [J. Chem. Phys. 136, 204119 (2012)] are presented. The SR tensors of both the H and X nuclei are discussed. Calculations were carried out within the relativistic Linear Response formalism at the Random Phase Approximation with the DIRAC program. For the halogen nucleus X, correlation effects on the non-relativistic values are shown to be of similar magnitude and opposite sign to relativistic effects. For the light H nucleus, by means of the linear response within the elimination of the small component approach it is shown that the whole relativistic effect is given by the spin-orbit operator combined with the Fermi contact operator. Comparison of "best estimate" calculated values with experimental results yield differences smaller than 2%-3% in all cases. The validity of "Flygare's relation" linking the SR tensor and the NMR nuclear magnetic shielding tensor in the present series of compounds is analyzed.

show abstract

Section: Discussion: Relativistic Corrections Lresc Expansion Anmentioning

confidence: 71%

“…39 Inserting these expressions in Eq. (22) and retaining terms bilinear in J (4) and A N it is found…”

Section: B Leading Relativistic Corrections Of the Spin-rotation Tenmentioning

confidence: 98%

“…The second order electronic contribution can be obtained by means of the relativistic 4-component linear response (lr) theory 22 at zero frequency, as the propagator…”

Section: A Relativistic 4-component Expression Of the Spin-rotation mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Theoretical study of the nuclear spin-molecular rotation coupling for relativistic electrons and non-relativistic nuclei. II. Quantitative results in HX (X=H,F,Cl,Br,I) compounds

Aucar

Gómez

Melo

et al. 2013

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…In this work we reconsider the prototypic van der Waals bonded system, the xenon dimer, and apply stateof-the-art four-component relativistic quantum-chemical methodology 16,17 to obtain predictions of J( 129 Xe − 131 Xe). Xenon isotopes are widely used as atomic guests, inert probes the NMR parameters of which are sensitive to the physical properties of the host material.…”

Section: J(mentioning

confidence: 99%

Nuclear spin-spin coupling in a van der Waals-bonded system: Xenon dimer

Vaara

Hanni

Jokisaari

2013

The Journal of Chemical Physics

View full text Add to dashboard Cite

Nuclear spin-spin coupling over van der Waals bond has recently been observed via the frequency shift of solute protons in a solution containing optically hyperpolarized 129 Xe nuclei. We carry out a first-principles computational study of the prototypic van der Waals-bonded xenon dimer, where the spin-spin coupling between two magnetically non-equivalent isotopes, J( 129 Xe − 131 Xe), is observable. We use relativistic theory at the four-component Dirac-Hartree-Fock and Diracdensity-functional theory levels using novel completeness-optimized Gaussian basis sets and choosing the functional based on a comparison with correlated ab initio methods at the nonrelativistic level. J-coupling curves are provided at different levels of theory as functions of the internuclear distance in the xenon dimer, demonstrating cross-coupling effects between relativity and electron correlation for this property. Calculations on small Xe clusters are used to estimate the importance of many-atom effects on J( 129 Xe − 131 Xe). Possibilities of observing J( 129 Xe − 131 Xe) in liquid xenon are critically examined, based on molecular dynamics simulation. A simplistic spherical model is set up for the xenon dimer confined in a cavity, such as in microporous materials. It is shown that the on the average shorter internuclear distance enforced by the confinement increases the magnitude of the coupling as compared to the bulk liquid case, rendering J( 129 Xe − 131 Xe) in a cavity a feasible target for experimental investigation.

show abstract

Correlated response calculations of the spin-orbit interaction contribution to nuclear spin-spin couplings

1999

View full text Add to dashboard Cite

Full four-component relativistic calculations of NMR shielding and indirect spin-spin coupling tensors in hydrogen halides

Cited by 190 publications

References 34 publications

Theoretical study of the nuclear spin-molecular rotation coupling for relativistic electrons and non-relativistic nuclei. II. Quantitative results in HX (X=H,F,Cl,Br,I) compounds

Theoretical study of the nuclear spin-molecular rotation coupling for relativistic electrons and non-relativistic nuclei. II. Quantitative results in HX (X=H,F,Cl,Br,I) compounds

Nuclear spin-spin coupling in a van der Waals-bonded system: Xenon dimer

Correlated response calculations of the spin-orbit interaction contribution to nuclear spin-spin couplings

Contact Info

Product

Resources

About