Density functional calculations of NMR shielding tensors for paramagnetic systems with arbitrary spin multiplicity: Validation on 3d metallocenes

Hrobárik, Peter; Reviakine, Roman; Arbuznikov, Alexei V.; Malkina, Olga L.; Malkin, Vladimir G.; Köhler, Frank H.; Kaupp, Martin
January 2007
Journal of Chemical Physics;1/14/2007, Vol. 126 Issue 2, p024107
Academic Journal
The calculation of nuclear shieldings for paramagnetic molecules has been implemented in the ReSpect program, which allows the use of modern density functional methods with accurate treatments of spin-orbit effects for all relevant terms up to order O(α4) in the fine structure constant. Compared to previous implementations, the methodology has been extended to compounds of arbitrary spin multiplicity. Effects of zero-field splittings in high-spin systems are approximately accounted for. Validation of the new implementation is carried out for the 13C and 1H NMR signal shifts of the 3d metallocenes 4VCp2, 3CrCp2, 2MnCp2, 6MnCp2, 2CoCp2, and 3NiCp2. Zero-field splitting effects on isotropic shifts tend to be small or negligible. Agreement with experimental isotropic shifts is already good with the BP86 gradient-corrected functional and is further improved by admixture of Hartree-Fock exchange in hybrid functionals. Decomposition of the shieldings confirms the dominant importance of the Fermi-contact shifts, but contributions from spin-orbit dependent terms are frequently also non-negligible. Agreement with 13C NMR shift tensors from solid-state experiments is of similar quality as for isotropic shifts.


Related Articles

  • First principle calculations of 113Cd chemical shifts for proteins and model systems. Hemmingsen, Lars; Olsen, Lars; Antony, Jens; Sauer, Stephan P. A. // Journal of Biological Inorganic Chemistry;Jul2004, Vol. 9 Issue 5, p591 

    113Cd isotropic NMR shieldings are calculated for a number of metal ion binding sites in proteins, using the GIAO-B3LYP and GIAO-HF methods with the uncontracted (19s15p9d4f) polarized basis set of Kellö and Sadlej on cadmium and 6-31G(d) on the ligands. The results compare favorably with...

  • Transition metal NMR chemical shifts from optimized effective potentials. Teale, Andrew M.; Cohen, Aron J.; Tozer, David J. // Journal of Chemical Physics;2/21/2007, Vol. 126 Issue 7, p074101 

    Metal shielding constants and chemical shifts are determined for nine transition metal complexes using an uncoupled formalism with orbitals and eigenvalues determined using the Yang-Wu implementation [W. Yang and Q. Wu, Phys. Rev. Lett. 89, 143002 (2002)] of the optimized effective potential...

  • Analysis of anisotropic effects in trinuclear metal carbonyl compounds by visualization of through-space NMR shielding. Araujo, Martha; Chacon, Eluzir; M. Carneiro, José; Koch, Andreas; Kleinpeter, Erich // Journal of Molecular Modeling;Aug2010, Vol. 16 Issue 8, p1415 

    Through-space NMR shieldings were calculated for trinuclear metal-carbonyl compounds [M3(CO)12] (M = Fe, Ru, Os), employing the nucleus-independent chemical shift approach. The through-space shieldings were visualized as a contour plot of iso-chemical shielding surfaces, and were applied to...

  • NMR Shielding and Spin-Rotation Constants of 175LuX (X = 19F, 35Cl, 79Br, 127I) Molecules. Demissie, Taye B. // AIP Conference Proceedings;2015, Vol. 1702, p1 

    This presentation demonstrates the relativistic effects on the spin-rotation constants, absolute nuclear magnetic resonance (NMR) shielding constants and shielding spans of 175LuX (X = 19F, 35Cl, 79Br, 127I) molecules. The results are obtained from calculations performed using density functional...

  • High-resolution solid-state NMR study of isotactic polypropylenes. Frcov�, O.; Uhr�nov�, M.; Hronsk�, V.; Koval'akov�, M.; Olc�k, D.; Chod�k, I.; Sp#v�cek, J. // Express Polymer Letters;2012, Vol. 6 Issue 3, p204 

    The high-resolution solid-state 13C NMR spectra were recorded for metallocene (m) and Ziegler-Natta (ZN) isotactic polypropylenes (iPP) in pelletized form using cross polarization (CP) and magic angle spinning (MAS) techniques within the temperature range of 20-160�C. Besides the CP MAS...

  • 129Xe chemical shift by the perturbational relativistic method: Xenon fluorides. Lantto, Perttu; Vaara, Juha // Journal of Chemical Physics;8/28/2007, Vol. 127 Issue 8, p084312 

    129Xe nuclear shielding tensor is calculated at the leading-order, one-electron Breit-Pauli perturbation theory (BPPT) level for the xenon fluorides XeF+, XeF2, XeF3+, and XeF4 that cover the large nuclear magnetic resonance chemical shift range of this nucleus. BPPT is found to improve the...

  • Relativistic effects on the nuclear magnetic resonance shielding of FX (X = F, Cl, Br, I, and At) molecular systems. Gómez, Sergio S.; Aucar, Gustavo A. // Journal of Chemical Physics;5/31/2011, Vol. 134 Issue 20, p204314 

    We present ab inito full four-component and spin-free calculations of the NMR shielding parameter, σ, in the FX (X = F, Cl, Br, I and At) molecular systems. A different expression that overcomes the traditional non-relativistic (NR) approximation used to calculate the relationship between...

  • Quadratic response calculations of the electronic spin-orbit contribution to nuclear shielding.... Vaara, Juha; Ruud, Kenneth // Journal of Chemical Physics;7/22/1998, Vol. 109 Issue 4, p1212 

    Examines the calculation of electronic spin-orbit contribution to nuclear shielding tensors. Contributions of Fermi contact to spin-orbit coupling; Neglect of scalar relativistic effects on deshielding effect; Comparison of [sup 13]carbon shielding anisotropies with nuclear magnetic resonance data.

  • Nuclei-selected NMR shielding calculations: A sublinear-scaling quantum-chemical method. Beer, Matthias; Kussmann, Jörg; Ochsenfeld, Christian // Journal of Chemical Physics;2/21/2011, Vol. 134 Issue 7, p074102 

    An ab initio method for the direct calculation of NMR shieldings for selected nuclei at the Hartree-Fock and density-functional theory level is presented. Our method shows a computational effort scaling only sublinearly with molecular size, as it is motivated by the physical consideration that...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics