Magnetic Resonance in Chemistry

Cover image for Vol. 48 Issue S1

Supplement: Quantum-Chemical Computations of Magnetic Resonance Parameters

December 2010

Volume 48, Issue S1

Pages S1–S175

Issue edited by: Sharon E. Ashbrook, Michael Böhl

  1. Editorials

    1. Top of page
    2. Editorials
    3. Reviews
    4. Research Articles
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  2. Reviews

    1. Top of page
    2. Editorials
    3. Reviews
    4. Research Articles
    1. First-principles calculation of parameters of electron paramagnetic resonance spectroscopy in solids (pages S2–S10)

      Eugene S. Kadantsev and Tom Ziegler

      Version of Record online: 5 SEP 2010 | DOI: 10.1002/mrc.2655

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      Methods for the first-principles calculation of the parameters of the electron paramagnetic resonance are reviewed. A full potential Kohn-Sham DFT-based approach for the calculation of hyperfine A- and Zeeman g-tensors in systems with periodic boundary conditions is developed. The robustness of the full potential scheme is demonstrated by considering a muonium defect in IIIA-VA zinc-blende semiconductors as well as the g-tensor of S2 anion radical in KCl host crystal lattice.

    2. An integrated computational protocol for the accurate prediction of EPR and PNMR parameters of aminoxyl radicals in solution (pages S11–S22)

      Vincenzo Barone, Paola Cimino and Alfonso Pedone

      Version of Record online: 12 JUL 2010 | DOI: 10.1002/mrc.2640

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      This review summarizes the results of systematic computational studies devoted to the calculation of EPR and PNMR parameters of aminoxyl radicals using methods rooted in the DFT and the N07D basis set.

    3. Prediction of NMR J-coupling in solids with the planewave pseudopotential approach (pages S23–S31)

      Jonathan R. Yates

      Version of Record online: 12 JUL 2010 | DOI: 10.1002/mrc.2646

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      We review the calculation of NMR J coupling in solid materials using the planewave pseudopotential formalism of Density Functional Theory. The methodology is briefly summarised and an account of recent applications is given. We discuss various aspects of the calculations which should be taken into account when comparing results with solid-state NMR experiments including; anisotropy and orientation of the J tensors, the reduced coupling constant, and the relation between J and crystal structure.

  3. Research Articles

    1. Top of page
    2. Editorials
    3. Reviews
    4. Research Articles
    1. A theoretical NMR study of ortho and para-substituted benzenes compared with silabenzenes, pyridines and phosphabenzenes (pages S32–S37)

      Ibon Alkorta and José Elguero

      Version of Record online: 19 MAR 2010 | DOI: 10.1002/mrc.2586

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      Calculations of absolute shieldings and NICS(1) values of 84 compounds (benzenes, silabenzenes, pyridines and phosphabenzenes) allowed to discuss the absolute shieldings in function of Brown σp+ substituent constant and to predict 71 new chemical shifts. The NICS(1) analysis of the aromaticity lead to the unexpected result for the silabenzenes, that it is almost insensitive to substituent effects. In these set of compounds, it can be concluded that aromaticity and its sensitivity to substituent effects are orthogonal.

    2. A comparison of experimental and DFT calculations of 195Pt NMR shielding trends for [PtXnY6−n]2− (X, Y = Cl, Br, F and I) anions (pages S38–S47)

      Marga R. Burger, J. Kramer, H. Chermette and Klaus R. Koch

      Version of Record online: 22 APR 2010 | DOI: 10.1002/mrc.2607

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      Comparison between experimental and calculated DFT 195Pt chemical shifts for [PtX6−nYn]2− complexes (X = Cl, Br, F, I) shows that discrepancies increase [PtCl6−nBrn]2− < [PtBr6−nIn]2− < [PtCl6−nIn]2− < [PtF6−nBrn]2−≈ [PtF6−nCln]2−, and are correlated with the electronegativity difference Δχ between the halide ions (X and Y) bound to Pt(IV). The computed 195Pt sensitivity to Pt-X bond displacement, ∂ (δ195Pt)/∂ (ΔPt-X) is large depending on the halide ion, decreasing from 24 800, 18 300, 15 700 to 12 000 ppm/Å for [PtF6]2−, [PtCl6]2−, [PtBr6]2− and [PtI6]2− respectively.

    3. Trivinylphosphine and trivinylphosphine chalcogenides: stereochemical trends of 31P[BOND]1H spin–spin coupling constants (pages S48–S55)

      Sergey V. Fedorov, Leonid B. Krivdin, Yury Yu. Rusakov, Nataliya A. Chernysheva and Valentina L. Mikhailenko

      Version of Record online: 12 MAY 2010 | DOI: 10.1002/mrc.2614

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      A combined theoretical and experimental study of the stereochemical behavior of 31P[BOND]1H spin–spin coupling constants has been performed in the series of trivinylphosphine and related trivinylphosphine oxide, sulfide and selenide. All 31P[BOND]1H spin–spin coupling constants involving phosphorus and either of the vinyl protons are found to demonstrate a marked stereochemical dependences with respect to the geometry of the coupling pathway and internal rotation of the vinyl group around the P[BOND]C bond.

    4. NMR chemical shifts as a tool to analyze first principles molecular dynamics simulations in condensed phases: the case of liquid water (pages S56–S60)

      Douglas R. Banyai, Tatiana Murakhtina and Daniel Sebastiani

      Version of Record online: 22 NOV 2010 | DOI: 10.1002/mrc.2620

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      The influence of computational parameters in Car-Parrinello molecular dynamics simulations on computed NMR chemical shifts can be significant. We gauge the impact of the choice of the exchange-correlation functional, hard versus soft pseudopotentials, and basis set convergence on 1H NMR chemical shifts in liquid water and give hints where to focus when setting up a molecular dynamics run.

    5. Density-functional computation of 93Nb NMR chemical shifts (pages S61–S68)

      Michael Bühl and Bernd Wrackmeyer

      Version of Record online: 15 JUN 2010 | DOI: 10.1002/mrc.2624

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      DFT methods are assessed for their capability to reproduce93Nb chemical shifts of a number of inorganic and organometallic Nb complexes. An inadvertent error in the reported δ(93Nb) values of some cyclopentadiene borane complexes is corrected.

    6. A computational investigation of J couplings involving 27Al, 17O, and 31P (pages S69–S75)

      David L. Bryce

      Version of Record online: 29 JUN 2010 | DOI: 10.1002/mrc.2630

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      Computations of 1J(27Al,17O), 1J(31P,17O), and 2J(31P,27Al) corroborate experimental results and provide potentially useful correlations between these coupling constants and the local structure in small molecules, grossite, and an aluminophosphate model system.

    7. Molecular orbital analysis of the inverse halogen dependence of nuclear magnetic shielding in LaX3, X = F, Cl, Br, I (pages S76–S85)

      Salvador Moncho and Jochen Autschbach

      Version of Record online: 29 JUN 2010 | DOI: 10.1002/mrc.2632

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      The NMR nuclear shielding tensors for the series LaX3, with X = F, Cl, Br and I, have been computed using two-component relativistic density functional theory based on the zeroth-order regular approximation (ZORA). A detailed analysis of the inverse halogen dependence (IHD) of the La shielding was performed via decomposition of the shielding tensor elements into contributions from localized and delocalized molecular orbitals.

    8. New perspectives in the PAW/GIPAW approach: JP-O-Si coupling constants, antisymmetric parts of shift tensors and NQR predictions (pages S86–S102)

      Christian Bonhomme, Christel Gervais, Cristina Coelho, Frédérique Pourpoint, Thierry Azaïs, Laure Bonhomme-Coury, Florence Babonneau, Guy Jacob, Maude Ferrari, Daniel Canet, Jonathan R. Yates, Chris J. Pickard, Siân A. Joyce, Francesco Mauri and Dominique Massiot

      Version of Record online: 29 JUN 2010 | DOI: 10.1002/mrc.2635

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      New insights into the calculation of NMR/NQR parameters using projected augmented wave and gauge including projected augmented wave approaches are proposed. Selected examples related to silicophosphates, explosives and cyclopropene derivatives illustrate these topics.

    9. Computation and NMR crystallography of terbutaline sulfate (pages S103–S112)

      Robin K. Harris, Paul Hodgkinson, Vadim Zorin, Jean-Nicolas Dumez, Bénédicte Elena-Herrmann, Lyndon Emsley, Elodie Salager and Robin S. Stein

      Version of Record online: 29 JUN 2010 | DOI: 10.1002/mrc.2636

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      GIPAW computations of 13C NMR spectra have been used to assess the validity of two crystal structure determinations for terbutaline sulfate Form B, and one structure is shown to be defective. Two– dimensional NMR experiments, in combination with the computations, were used to assign signals to crystallographic atomic positions and probe hydrogen– bonding motifs.

    10. Comparing quantum-chemical calculation methods for structural investigation of zeolite crystal structures by solid-state NMR spectroscopy (pages S113–S121)

      Darren H. Brouwer, Igor L. Moudrakovski, Richard J. Darton and Russell E. Morris

      Version of Record online: 12 JUL 2010 | DOI: 10.1002/mrc.2642

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      Using recently acquired ultrahigh-field 29Si NMR data for the pure silica zeolite ITQ-4, we report the results of calculations of 29Si chemical shielding tensors using plane-wave density functional theory methods for periodic crystalline solids (as implemented in CASTEP) and compare to calculations on extracted molecular clusters performed with Gaussian. We also report the completion of the NMR crystallography of the zeolite ITQ-4 by exploring a number of structure refinement approaches involving quantum-chemical calculations.

    11. Calculation of the 4,5-dihydro-1,3,2-dithiazolyl radical g tensor components by the coupled-perturbed Kohn–Sham hybrid density functional and configuration interaction methods: a comparative study (pages S122–S131)

      Saba M. Mattar and Jeremy Durelle

      Version of Record online: 12 JUL 2010 | DOI: 10.1002/mrc.2649

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      The 4,5-dihydro-1,3,2-dithiazolyl radical g tensor is calculated by hybrid density functional (HDF) and multi-reference configuration interaction-sum over states (MRCI-SOS) methods. The tensor components are in very good agreement (1000 ppm) with those determined experimentally by electron paramagnetic resonance (EPR) spectroscopy. Although more costly, the MRCI technique, that includes the in-plane and out-of-plane interactions in a unbiased way, produced g tensor components that are more accurate than those obtained by the HDF method.

    12. Predicting the 1H and 13C NMR spectra of paramagnetic Ru(III) complexes by DFT (pages S132–S141)

      Federico Rastrelli and Alessandro Bagno

      Version of Record online: 5 SEP 2010 | DOI: 10.1002/mrc.2666

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      The 1H NMR spectra of paramagnetic Ru(III) complexes are characterized by sharper line widths than most other transition metals, and are therefore easier to obtain. Contact shifts are still ‘unpredictable’, however. DFT calculations of magnetic properties (contact and pseudocontact shifts, relaxation rates) allow one to make such predictions in a useful manner.

    13. First-principles calculations of NMR parameters for phosphate materials (pages S142–S150)

      Filipe Vasconcelos, Sylvain Cristol, Jean-François Paul, Lionel Montagne, Francesco Mauri and Laurent Delevoye

      Version of Record online: 5 SEP 2010 | DOI: 10.1002/mrc.2667

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      We discuss the ability to reproduce NMR parameters in the case of phosphates materials through electronic structure calculation within density functional theory linear response, using the gauge-including projector-augmented wave. We emphasise on the crucial points, i.e. electronic structure and geometry, that should be considered to perform such calculations. Experimental and theoretical comparison of 31P, 1H and 23Na NMR data on a series of sodium phosphate systems are presented to illustrate the review.

    14. Difference between 2JC2H3 and 2JC3H2 spin–spin couplings in heterocyclic five- and six-membered rings as a probe for studying σ-ring currents: a quantum chemical analysis (pages S151–S158)

      Rubén H. Contreras, Francisco P. dos Santos, Lucas C. Ducati and Cláudio F. Tormena

      Version of Record online: 5 SEP 2010 | DOI: 10.1002/mrc.2669

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      Adequate analyses of canonical molecular orbitals (CMOs) can provide rather detailed information on the importance of different σ-Fermi contact (FC) coupling pathways. Their relative importance for transmitting the σ-FC contribution to a given spin–spin coupling is estimated by resorting to the expression of the FC term given by the polarization propagator formalism. Significant differences between the FC terms of 2JC2H3 and 2JC3H2 are taken as probes to gauge the differences in σ-ring currents for the five- and six-membered rings.

    15. Contribution of first-principles calculations to multinuclear NMR analysis of borosilicate glasses (pages S159–S170)

      Anne Soleilhavoup, Jean-Marc Delaye, Frédéric Angeli, Daniel Caurant and Thibault Charpentier

      Version of Record online: 5 SEP 2010 | DOI: 10.1002/mrc.2673

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      Molecular dynamics simulations are combined with DFT GIPAW-NMR calculations to devise novel procedures to process and interpret the solid-state NMR data acquired on binary borosilicate glasses. Important information on the structure such as bond angles distribution can then be estimated.

    16. Electric field gradient calculations in paramagnetic compounds using the PAW approach. Application to 23Na NMR in layered vanadium phosphates (pages S171–S175)

      J. Cuny, J.R. Yates, R. Gautier, E. Furet, E. Le Fur and L. Le Pollès

      Version of Record online: 5 SEP 2010 | DOI: 10.1002/mrc.2674

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      EFG values measured by 23Na NMR experiments were reproduced with a level of accuracy comparable to the one achievable in diamagnetic compounds and allowed the assignment of observed 23Na NMR signals. This work demonstrates the ability of a periodic PAW-based approach for the calculation of EFG parameters in paramagnetic compounds.

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