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Fully relativistic theories and methods for NMR parameters

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Abstract

Nuclear magnetic shielding and spin–spin coupling constants are intrinsically all-electron relativistic properties and demand in principle fully relativistic treatments. Here, the magnetic balance (MB) condition plays an essential role, both conceptually and computationally. The various formulations can be unified in terms of the idea of "orbital decomposition." Further combined with the ansatz of "gauge-including atomic orbitals" (GIAO) for distributed gauge origins leads to very efficient four-component relativistic methods at both the mean-field and correlated levels. To illustrate the latter, the no-pair MB-GIAO-MP2 expressions for nuclear shieldings are derived in two different ways, one with the derivative technique and the other through the induced current. Due to the non-variational nature of MP2, the two expressions are not identical. The current-dependent expression is much simpler and appears more natural in view of the experimental measurement.

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Notes

  1. Equation 34 in Ref. [17] turns out to be inappropriate and should be replaced with the present Eq. 61.

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Acknowledgments

The research of this work was supported by grants from the National Natural Science Foundation of China (Project No. 21033001). W.L. is grateful to Prof. Dr. Ch. van Wüllen for the invitation and stimulating discussions.

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Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences, Institute of Theoretical and Computational Chemistry, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, and Center for Computational Science and Engineering, Peking University, Beijing, 100871, People’s Republic of China

    Yunlong Xiao, Qiming Sun & Wenjian Liu

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  1. Yunlong Xiao
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  2. Qiming Sun
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  3. Wenjian Liu
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Correspondence to Wenjian Liu.

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Published as part of the special collection of articles celebrating the 50th anniversary of Theoretical Chemistry Accounts/Theoretica Chimica Acta.

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Xiao, Y., Sun, Q. & Liu, W. Fully relativistic theories and methods for NMR parameters. Theor Chem Acc 131, 1080 (2012). https://doi.org/10.1007/s00214-011-1080-z

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