Quantum-Chemical Approach to NMR Chemical Shifts in Paramagnetic Solids Applied to LiFePO<sub>4</sub> and LiCoPO<sub>4</sub>

Mondal, Arobendo; Kaupp, Martin

doi:10.1021/acs.jpclett.8b00407

Cited by 30 publications

(50 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Relativistic effects in NMR chemical shifts and spin–spin coupling constants known as “Heavy Atom on Light Atom” (HALA) effects were evaluated in a great number of molecules containing “heavy” elements, see some salient earlier publications together with some more recent and most recent ones and many other related papers, which are not cited herewith in full in view of their multiplicity.…”

Section: Theoretical Methods and Accuracy Factorsmentioning

confidence: 99%

“…Relativistic effects in NMR chemical shifts and spinspin coupling constants known as "Heavy Atom on Light Atom" (HALA) effects were evaluated in a great number of molecules containing "heavy" elements, see some salient earlier publications [117][118][119][120][121][122][123][124][125][126] together with some more recent and most recent ones [127][128][129][130][131][132][133][134][135][136][137][138][139][140][141][142][143][144][145] and many other related papers, [146][147][148][149][150][151][152][153][154][155] which are not cited herewith in full in view of their multiplicity.…”

Section: Figurementioning

confidence: 99%

See 1 more Smart Citation

Computational ¹H NMR: Part 1. Theoretical background

Krivdin

2019

Magnetic Reson in Chemistry

View full text Add to dashboard Cite

This is the first one of the three closely interrelated reviews to be published in Magnetic Resonance in Chemistry dealing with accordingly theoretical background, chemical applications, and biochemical studies of and by means of computational 1H NMR. Presented in the first part of the review is a general outline of the modern theoretical methods and accuracy factors of computational 1H NMR involving locally dense basis set schemes, solvent effects, vibrational corrections, and relativistic effects performed at the density functional theory and/or nonempirical levels. This review is dedicated to Prof. Stephan Sauer in view of his invaluable contribution to the field of computational nuclear magnetic resonance.

show abstract

Section: Theoretical Methods and Accuracy Factorsmentioning

confidence: 99%

Section: Figurementioning

confidence: 99%

Computational ¹H NMR: Part 1. Theoretical background

Krivdin

2019

Magnetic Reson in Chemistry

View full text Add to dashboard Cite

show abstract

“…48 It is well known that standard DFT functionals dramatically underestimate the magnitude of zero-field splitting (ZFS, D-tensor) in high-spin Co II complexes and correlated multi-reference wave-function level of electronic structure theory is needed for reliable results. [49][50][51] Here, the spin-orbit part of the D-tensor was evaluated using quasi-degenerate perturbation theory (QDPT) 52 applied to the NEVPT2 electronic structure (see the calculated values in Table S3). A test CAS-CI calculation with the converged SA-CASSCF(7,5) wave-function was performed to confirm that the spin-spin part of the D-tensor is in this case negligible with all DSS matrix elements being smaller than 0.15 cm -1 .…”

Section: Quantum Chemistry Modelingmentioning

confidence: 99%

Picometer Resolution Structure of the Coordination Sphere in the Metal-Binding Site in a Metalloprotein by NMR

et al. 2020

Self Cite

View full text Add to dashboard Cite

Most of our understanding of chemistry derives from atomic-level structures obtained with single crystal X-ray diffraction. Metal centers in X-ray structures of small organometallic or coordination complexes are often extremely well defined, with errors in the positions on the order of 10-4-10-5 Å. Determining the metal coordination geometry to high accuracy is essential for understanding metal center reactivity, as even small structural changes can dramatically alter the metal activity. In contrast, the resolution of X-ray structures in proteins is limited typically to the order of 10-1 Å. This resolution is often not sufficient to develop precise structure-activity relations for the metal sites in proteins, since the uncertainty in positions can cover all the known ranges of bond-lengths and bond-angles for a given type of metal-complex. Here we introduce a new approach that enables determination of a high-definition structure of the active site of a metalloprotein from a powder sample, by combining magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy, tailored radio-frequency (RF) irradiation schemes, and computational approaches. This allows us to overcome the "blind sphere" in paramagnetic proteins, and to observe and assign 1 H, 13 C, and 15 N resonances for the ligands directly coordinating the metal center. We illustrate the method by determining the bond lengths in the structure of the Co II coordination sphere at the core of human superoxide dismutase 1 (SOD) with 0.7 pm precision. The coordination geometry of the resulting structure explains the non-reactive nature of the Co II /Zn II centers in these proteins, that allows them to play a purely structural role.

show abstract

“…2.34 to NMR shielding for paramagnetic solids to include ZFS can be obtained by including ZFS and taking the g-tensor and ZFS contributions from the neighboring spin centers into account (see below) based on eq. 2.26, 123,151…”

Section: Chapter 2 Theorymentioning

confidence: 99%

“…Here we apply this advanced formalism 148,151,310 to the first systematic studies of partially delithiated vanadium phosphates. In these computations we do not only include the FC shifts arising from isotropic hyperfine-couplings (HFC) but also account for the combined effects of the anisotropic parts of HFC, g-tensor, and D-tensor leading to PC shifts and * Chapter 6 as well as tables and graphics within are reproduced in part with permission from A.…”

Section: Introductionmentioning

confidence: 99%

Probing Interactions of N-Donor Molecules with Open Metal Sites within Paramagnetic Cr-MIL-101: A Solid-State NMR Spectroscopic and Density Functional Theory Study

et al. 2018

Self Cite

View full text Add to dashboard Cite

Understanding host-guest interactions is one of the key requirements for adjusting properties in metal-organic frameworks (MOFs). In particular, systems with coordinatively unsaturated Lewis acidic metal sites feature highly selective adsorption processes. This is attributed to strong interactions with Lewis basic guest molecules. Here we show that a combination of C MAS NMR spectroscopy with state-of-the-art density functional theory (DFT) calculations allows one to unravel the interactions of water, 2-aminopyridine, 3-aminopyridine, and diethylamine with the open metal sites in Cr-MIL-101. TheC MAS NMR spectra, obtained with ultrafast magic-angle spinning, are well resolved, with resonances distributed over 1000 ppm. They present a clear signature for each guest at the open metal sites. Based on competition experiments this leads to the following binding preference: water < diethylamine ≈ 2-aminopyridine < 3-aminopyridine. Assignments were done by exploiting distance sum relations derived from spin-lattice relaxation data and C{H} REDOR spectral editing. The experimental data were used to validate NMR shifts computed for the Cr-MIL-101 derivatives, which contain CrO clusters with magnetically coupled metal centers. While both approaches provide an unequivocal assignment and the arrangement of the guests at the open metal sites, the NMR data offer additional information about the guest and framework dynamics. We expect that our strategy has the potential for probing the binding situation of adsorbate mixtures at the open metal sites of MOFs in general and thus accesses the microscopic interaction mechanisms for this important material class, which is essential for deriving structure-property relationships.

show abstract

Quantum-Chemical Approach to NMR Chemical Shifts in Paramagnetic Solids Applied to LiFePO₄ and LiCoPO₄

Cited by 30 publications

References 32 publications

Computational ¹H NMR: Part 1. Theoretical background

Computational ¹H NMR: Part 1. Theoretical background

Picometer Resolution Structure of the Coordination Sphere in the Metal-Binding Site in a Metalloprotein by NMR

Probing Interactions of N-Donor Molecules with Open Metal Sites within Paramagnetic Cr-MIL-101: A Solid-State NMR Spectroscopic and Density Functional Theory Study

Contact Info

Product

Resources

About

Quantum-Chemical Approach to NMR Chemical Shifts in Paramagnetic Solids Applied to LiFePO4 and LiCoPO4

Cited by 30 publications

References 32 publications

Computational 1H NMR: Part 1. Theoretical background

Computational 1H NMR: Part 1. Theoretical background

Picometer Resolution Structure of the Coordination Sphere in the Metal-Binding Site in a Metalloprotein by NMR

Probing Interactions of N-Donor Molecules with Open Metal Sites within Paramagnetic Cr-MIL-101: A Solid-State NMR Spectroscopic and Density Functional Theory Study

Contact Info

Product

Resources

About

Quantum-Chemical Approach to NMR Chemical Shifts in Paramagnetic Solids Applied to LiFePO₄ and LiCoPO₄

Computational ¹H NMR: Part 1. Theoretical background

Computational ¹H NMR: Part 1. Theoretical background