University of Oulu

Paramagnetic NMR chemical shift theory : combined ab initio/density-functional theory method

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Author: Rouf, Syed Awais1
Organizations: 1University of Oulu, Faculty of Science, Physics
Format: ebook
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 18.2 MB)
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Language: English
Published: 2017
Publish Date: 2017-10-06
Thesis type: Doctoral Dissertation
Defence Note: Academic dissertation to be presented with the assent of the Doctoral Training Committee of Technology and Natural Sciences of the University of Oulu for public discussion in the Auditorium L10, Linnanmaa, on October 13th, 2017, at 12 o’clock noon.
Tutor: Professor Juha Vaara
Doctor Jiří Mareš
Reviewer: Professor Radek Marek
Doctor Michael Patzschke
Opponent: Professor Tapio Rantala,
Kustos: Professor Juha Vaara


In this thesis, the classic Kurland-McGarvey theory for the nuclear magnetic resonance (NMR) chemical shift is presented in a modern framework for paramagnetic systems containing one or more unpaired electrons. First-principles computations are carried out for the NMR shielding tensors in paramagnetic transition-metal complexes. A combined ab initio/density-functional theory (DFT) approach is applied to obtain the necessary electron paramagnetic resonance (EPR) property tensors, i.e., the g-tensor, zero-field splitting tensor (D) and hyperfine coupling tensors (A). In DFT, both the generalised-gradient approximation and hybrid DFT are applied to calculate A. The complete active space self-consistent field theory (CASSCF) and N-electron valence-state perturbation theory (NEVPT2) are applied to calculate the g- and D-tensors. Scalar relativistic effects are included at the second-order Douglas-Kroll-Hess level for the g- and D-tensors and, for A, at the fully relativistic four-component matrix-Dirac-Kohn-Sham level. This methodology is applied to study ¹³C and ¹H chemical shifts and shielding anisotropies in a series of Co(II) pyrazolylborate complexes, a Cr(III) quinolyl-functionalised cyclopentadienyl complex, Ni(II) acetylacetonate complexes and various metallocenes.

The results obtained from these calculations are generally in a good agreement with the experimental data, in some cases, for Ni(II) complexes, allowing to correct the experimental spectral signal assignment. CASSCF/NEVPT2 computations (especially for the D-tensor) are more accurate than DFT, which is useful for the purpose of obtaining the NMR chemical shifts. The computational results obtained are dependent on the choice of molecular geometry (experimental X-ray or computationally optimised), wavefunction used for g and D (CASSCF or NEVPT2), DFT functional for A, and the quality of the basis sets. The locally dense basis method used for the CASSCF/NEVPT2 computations is less expensive and gives equally good results for g and D as fully balanced basis sets. The scalar relativistic influences are usually small for g and D, but are large for A. Due to that, scalar relativistic effects are important for the chemical shift and shielding anisotropy, especially for carbon nuclei.

These first-principles computations based on combined ab initio/DFT methodology are promising for the treatment of important electron correlation and scalar relativistic effects in the calculation of pNMR chemical shifts and shielding anisotropies. This work provides a straightforward platform for further development of pNMR shielding theory in terms of first-principles wavefunctions, as well as for applications in current problems in bio- and materials sciences, including low-temperature experiments.

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Osajulkaisut / Original papers

Osajulkaisut eivät sisälly väitöskirjan elektroniseen versioon / Original papers are not included in the electronic version of the dissertation.

  1. Vaara, J., Rouf, S. A., & Mareš, J. (2015). Magnetic Couplings in the Chemical Shift of Paramagnetic NMR. Journal of Chemical Theory and Computation, 11(10), 4840–4849.

  2. Rouf, S. A., Mareš, J., & Vaara, J. (2015). ¹H Chemical Shifts in Paramagnetic Co(II) Pyrazolylborate Complexes: A First-Principles Study. Journal of Chemical Theory and Computation, 11(4), 1683–1691.

  3. Rouf, S. A., Jakobsen, V. B., Mareš, J., Jensen, N. D., McKenzie, C. J., Vaara, J., & Nielsen, U. G. (2017). Assignment of solid-state ¹³C and ¹H NMR spectra of paramagnetic Ni(II) acetylacetonate complexes aided by first-principles computations. Solid State Nuclear Magnetic Resonance, 87, 29–37.

    Rinnakkaistallennettu versio / Self-archived version

  4. Rouf, S. A., Mareš, J., & Vaara, J. (2017). Relativistic Approximations to Paramagnetic NMR Chemical Shift and Shielding Anisotropy in Transition Metal Systems. Journal of Chemical Theory and Computation, 13(8), 3731–3745.

    Rinnakkaistallennettu versio / Self-archived version

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Series: Report series in physical sciences
ISSN: 1239-4327
ISSN-L: 1239-4327
ISBN: 978-952-62-1685-0
ISBN Print: 978-952-62-1684-3
Issue: 114
Copyright information: © University of Oulu, 2017. This publication is copyrighted. You may download, display and print it for your own personal use. Commercial use is prohibited.