Fermi Contact Shifts Research Articles

Dipolar dephasing for structure determination in a paramagnetic environment

We demonstrate the efficacy of the REDOR-type sequences in determining dipolar coupling strength in a paramagnetic environment. Utilizing paramagnetic effects of enhanced relaxation rates and rapid electronic fluctuations in Cu(II)-(DL-Ala)2.H2O, the dipolar coupling for the methyl C–H that is 4.20 ​Å (methyl carbon) away from the Cu2+ ion, was estimated to be 8.8 ​± ​0.6 ​kHz. This coupling is scaled by a factor of ~0.3 in comparison to the rigid limit value of ~32 ​kHz, in line with partial averaging of the dipolar interaction by rotational motion of the methyl group. Limited variation in the scaling factor of the dipolar coupling strength at different temperatures is observed. The C–H internuclear distance derived from the size of the dipolar coupling is similar to that observed in the crystal structure. The errors in the dipolar coupling strength observed in the REDOR-type experiments are similar to those reported for diamagnetic systems. Increase in resolution due to the Fermi contact shifts, coupled with MAS frequencies of 30–35 ​kHz allowed to estimate the hyperfine coupling strengths for protons and carbons from the temperature dependence of the chemical shift and obtain a high resolution 1H–1H spin diffusion spectrum. This study shows the utility of REDOR-type sequences in obtaining reliable structural and dynamical information from a paramagnetic complex. We believe that this can help in studying the active site of paramagnetic metalloproteins at high resolution.

Experimental 1H and 13C Solid-State NMR Signal Assignment of Paramagnetic Copper (II) 2-Pyrazine-Carboxylate Complex using Density Functional Theory Calculations

We have acquired 1H and 13C solid-state NMR (ssNMR) spectra of the paramagnetic Cu(II)-2-pyrazine-carboxylate (Cu-Py) complex and assigned paramagnetic 1H/13C signals using density functional theory (DFT) calculations. The unpaired electron in Cu(II) ionexacerbates the 1H and 13C chemical shifts in the Cu-Py complex through hyperfine interactions, making the conventional NMR signal assignment non-feasible. Further, the nuclear fast relaxation in paramagnetic metal-organic system hampers application of routine ssNMR techniques for signal acquisition. In our work we have employed simple DEPTH experiment at 50 kHz magic angle spinning (MAS) for acquiring 1H and 13C 1D ssNMR spectra of the paramagnetic Cu(II)-2-pyrazine-carboxylate (Cu-Py) complex. The paramagnetic augmented (diamagnetic chemical shift + paramagnetic shift) 1D 1H and 13C ssNMR signals (shifts) from Cu-Py complex have major contribution from Fermi contact interaction due to proximity of the organic arm to Cu2+ ion (Cu2+-C/H atoms 0-5 Å). The unpaired electron spin density distributed over the pyrazine-carboxylate organic arm is crucial in understanding Fermi contact shifts and hence accounts for 1H and 13C ssNMR signal assignment. The theoretical Fermi contact shifts together with diamagnetic shifts, calculated using density functional theory (DFT) at B3LYP level with basis sets viz. 6-311G, 6-311G+(D) and 6-311G++(D), were compared with the experimental shifts to facilitate the process of signal assignment. Vibrational analysis of Cu-Py complex was performed at B3LYP level of theory with various basis sets in comparison with experimental IR data. This further assisted in double validation of DFT optimized Cu-Py structure used here for extracting Fermi contact shifts. Furthermore molecular orbital analysis on the DFT optimized Cu-Py structure articulates the spin density distribution mechanism, thereby stipulating the location of the unpaired electron in the Cu(II) dx 2 -y 2 orbital in Paramagnetic Cu-Py complex.

Local atomic and electronic structure in the LiVPO4 (F,O) tavorite-type materials from solid-state NMR combined with DFT calculations.

7 Li, 31 P, and 19 F solid-state nuclear magnetic resonance (NMR) spectroscopy was used to investigate the local arrangement of oxygen and fluorine in LiVPO4 F1-y Oy materials, interesting as positive electrode materials for Li-ion batteries. From the evolution of the 1D spectra versus y, 2D 7 Li radiofrequency-driven recoupling (RFDR) experiments combined, and a tentative signal assignment based on density functional theory (DFT) calculations, it appears that F and O are not randomly dispersed on the bridging X position between two X-VO4 -X octahedra (X = O or F) but tend to segregate at a local scale. Using DFT calculations, we analyzed the impact of the different local environments on the local electronic structure. Depending on the nature of the VO4 X2 environments, vanadium ions are either in the +III or in the +IV oxidation state and can exhibit different distributions of their unpaired electron(s) on the d orbitals. Based on those different local electronic structures and on the computed Fermi contact shifts, we discuss the impact on the spin transfer mechanism on adjacent nuclei and propose tentative signal assignments. The O/F clustering tendency is discussed in relation with the formation of short VIV O vanadyl bonds with a very specific electronic structure and possible cooperative effect along the chain.

Optimizing the Ueff value for DFT+U calculation of paramagnetic solid-state NMR shifts by double Fermi-contact-shift verification

The isotropic chemical shifts can be calculated by hybrid functionals, which costs lots of computational resources. To save time, DFT+U could be employed to calculate the isotropic chemical shifts. However, the calculated properties are very sensitive to the Hubbard correction value Ueff. Here the double Fermi-contact-shift verification approach with DFT+U method is proposed with much higher computational efficiency, that is, concurrently calculate the Fermi-contact shifts on two nuclei (6Li and 17O) to predict the optimal Ueff. The optimal Ueff is also helpful to the quadrupolar coupling constant CQ, g-factor, band structure and density of states.

A New Class of Lanthanide Complexes with Three Ligand Centered Radicals: NMR Evaluation of Ligand Field Energy Splitting and Magnetic Coupling.

Combination of three radical anionic Ph-BIAN ligands (Ph-BIAN=bis-(phenylimino)-acenaphthenequinone) with lanthanoid ions leads to a series of homoleptic, six-coordinate complexes of the type Ln(Ph-BIAN)3 . Magnetic coupling data were measured by paramagnetic solution NMR spectroscopy. Combining 1 H NMR with 2 H NMR of partially deuterated compounds allowed a detailed study of the magnetic susceptibility anisotropies over a large temperature range. The observed chemical shifts were separated into ligand- and metal-centered contributions by comparison with the Y analogue (diamagnetic at the metal). The metal-centered contributions of the complexes with the paramagnetic ions could then be separated into pseudocontact and Fermi contact shifts. The latter is large within the Ph-BIAN scaffold, which shows that magnetic coupling is significant between the lanthanide ion and the radical ligand. Pseudocontact shifts were further correlated to structural data obtained from X-ray diffraction experiments. Ligand-field parameters were determined by fitting the temperature dependence of the observed magnetic susceptibility anisotropies. The electronic structure determined by this approach shows, that the Er and Tm analogues are candidates for single molecule magnets (SMM). These results demonstrate the possibilities for the application of NMR spectroscopy in investigations of paramagnetic systems in general and single molecule magnets in particular.

Combining HFEPR and NMR Spectroscopies to Characterize Organochromium(III) Complexes with Large Zero-Field Splitting

A series of three organochromium(III) complexes, based on a quinoline-substituted cyclopentadienyl ring coordinated to a CrCl2 moiety—C5Me4(C9NH6)CrCl2 (1), C5Ph4(C9NH6)CrCl2 (2), and C5Me4(C11NH10)CrCl2 (3)—has been investigated by EPR spectroscopy, including high-frequency and -field EPR (HFEPR) as well as by 1H NMR. Complex 3 is new and has higher solubility than 1 and 2, which could potentially improve its activity as an alkene polymerization precatalyst, an application that has already been documented for 1 and 2. The HFEPR studies show that 1–3 exhibit zero-field splitting (zfs) that is unusually large for Cr(III) (3d3, S = 3/2), as given by the axial zfs parameter D ≥ ∼3 cm–1. The zfs determined here for 1 is in good agreement with previous theoretical studies of this complex by other workers, which were made in the absence of any knowledge of the experimental data. Such a “blind” comparison of theory and experiment is very rare. The NMR spectra of 3 are fully analyzed using the zfs data and clearly show the dominant contribution of Fermi contact shifts, now that the pseudocontact (dipolar) shifts can be accurately determined. The results show the power of integrated magnetic resonance (EPR and NMR) spectroscopy combined with theoretical calculations in understanding the subtleties of electronic structure of the paramagnetic organometallic complex, in this case with S > 1/2, which could then be related to chemical reactivity or magnetic properties.

Study of Defect Chemistry in the System La2–xSrxNiO4+δ by 17O Solid-State NMR Spectroscopy and Ni K-Edge XANES

The properties of mixed ionic–electronic conductors (MIECs) are most conveniently controlled through site-specific aliovalent substitution, yet few techniques can report directly on the local structure and defect chemistry underpinning changes in ionic and electronic conductivity. In this work, we perform high-resolution 17O (I = 5/2) solid-state NMR spectroscopy of La2–xSrxNiO4+δ, an MIEC and prospective solid oxide fuel cell (SOFC) cathode material, showing the sensitivity of 17O hyperfine (Fermi contact) shifts and quadrupolar coupling constants due to local structural changes arising from Sr substitution (x). Previously, we resolved resonances from three distinct oxygen sites (interstitial, axial, and equatorial) in the unsubstituted x = 0 material (Halat et al., J. Am. Chem. Soc. 2016, 138, 11958). Here, substitution-induced changes in these three spectral features indirectly report on the ionic conductivity, local octahedral tilting, and electronic conductivity, respectively, of the (substituted) ma...

Understanding Local Defects in Li-Ion Battery Electrodes through Combined DFT/NMR Studies: Application to LiVPO4F

In a recent study, we showed by solid-state NMR that LiVPO4F, which is a promising material as positive electrode for Li-ion batteries, often exhibits some defects that may affect its electrochemical behavior. In this paper, we use DFT calculations based on the projector augmented-wave (PAW) method in order to model possible defects in this (paramagnetic) material and to compute the Fermi contact shifts expected for Li nuclei located in their proximity. The advantage of the PAW approach versus FP-LAPW we have been previously using is that it allows considering large supercells suitable to model a diluted defect. In the first part of this paper, we aim to validate the Fermi contact shifts calculation using the PAW approach within the VASP code. Then we apply this strategy for modeling possible defects in LiVPO4F. By analogy with the already existing homeotypic LiVOPO4 phase, we first replace one fluoride ion, along the VO2F4 chains, by an oxygen one and consider, in a second step, an association with a lit...

Probing Oxide-Ion Mobility in the Mixed Ionic-Electronic Conductor La2NiO4+δ by Solid-State (17)O MAS NMR Spectroscopy.

While solid-state NMR spectroscopic techniques have helped clarify the local structure and dynamics of ionic conductors, similar studies of mixed ionic–electronic conductors (MIECs) have been hampered by the paramagnetic behavior of these systems. Here we report high-resolution 17O (I = 5/2) solid-state NMR spectra of the mixed-conducting solid oxide fuel cell (SOFC) cathode material La2NiO4+δ, a paramagnetic transition-metal oxide. Three distinct oxygen environments (equatorial, axial, and interstitial) can be assigned on the basis of hyperfine (Fermi contact) shifts and quadrupolar nutation behavior, aided by results from periodic DFT calculations. Distinct structural distortions among the axial sites, arising from the nonstoichiometric incorporation of interstitial oxygen, can be resolved by advanced magic angle turning and phase-adjusted sideband separation (MATPASS) NMR experiments. Finally, variable-temperature spectra reveal the onset of rapid interstitial oxide motion and exchange with axial sites at ∼130 °C, associated with the reported orthorhombic-to-tetragonal phase transition of La2NiO4+δ. From the variable-temperature spectra, we develop a model of oxide-ion dynamics on the spectral time scale that accounts for motional differences of all distinct oxygen sites. Though we treat La2NiO4+δ as a model system for a combined paramagnetic 17O NMR and DFT methodology, the approach presented herein should prove applicable to MIECs and other functionally important paramagnetic oxides.

Paramagnetic NMR Analysis of Substituted Biscyclooctatetraene Lanthanide Complexes

Cyclooctatetraene derivatives (COTR) with two carbocycles attached to the central ring have been used as dianionic ligands for the synthesis of double-decker complexes of the type [(COTR)2M]−. Two ligand derivatives were combined with diamagnetic Y3+ and with the five paramagnetic lanthanide ions from Tb3+ to Tm3+. The more complex substitution pattern in comparison to the parent ligand COT or the popular bis-trimethylsilyl derivative allows a sufficient number of signals to be obtained for a comprehensive paramagnetic NMR analysis. The anionic double-decker complexes gave well-resolved NMR spectra where almost all 1H and 13C NMR signals could be detected and assigned. With these data, it was possible to separate the two main contributions to the paramagnetic shift (pseudocontact and Fermi contact shifts, respectively) and to determine the magnetic anisotropy of the lanthanide ions in their ligand fields. We can easily obtain the sign and the magnitude of the anisotropy of the magnetic susceptibility, whi...

Ligand π-radical interaction with f-shell unpaired electrons in phthalocyaninato-lanthanoid single-molecule magnets: a solution NMR spectroscopic and DFT study.

The phthalocyaninato double-decker complexes [M(obPc)2 ](0) (M= Y(III) , Tb(III) , Dy(III) ; obPc=2,3,9,10,16,17,23,24-octabutoxyphthalocyaninato), along with their reduced ([M(obPc)2 ](-) [P(Ph)4 ](+) ; M=Tb(III) , Dy(III) ) and oxidized ([M(obPc)2 ](+) [SbCl6 ](-) (M=Y(III) , Tb(III) ) counterparts were studied with (1) H, (13) C and 2D NMR. From the NMR data of the neutral (i.e., with one unpaired electron in the ligands) and anionic Tb(III) complexes, along with the use of dispersion corrected DFT methods, it was possible to separate the metal-centered and ligand-centered contributions to the hyperfine NMR shift. These contributions to the (1) H and (13) C hyperfine NMR shifts were further analyzed in terms of pseudocontact and Fermi contact shifts. Furthermore, from a combination of NMR data and DFT calculations, we have determined the spin multiplicity of the neutral complexes [M(obPc)2 ](0) (M=Tb(III) and Dy(III) ) at room temperature. From the NMR data of the cationic Tb(III) complex, for which actually no experimental structure determination is available, we have analyzed the structural changes induced by oxidation from its neutral/anionic species and shown that the interligand distance decreases upon oxidation. The fast electron exchange process between the neutral and anionic Tb(III) double-decker complexes was also studied.

Solid‐State NMR Characterization of Paramagnetic Bis(L‐valinato)copper(II) Stereoisomers – Effect of Conformational Disorder and Molecular Mobility on 13C and 2H Fast Magic‐Angle Spinning Spectra

AbstractThe solid‐state 13C and 2H NMR spectra of paramagnetic anhydrous trans‐bis(L‐valinato)copper(II) and cis‐aquabis(L‐valinato)copper(II) complexes have been obtained. Under the very fast MAS conditions, both the 13C and 2H MAS spectra were well enough resolved to allow the easy distinction between the trans and cis stereoisomers. The conformational disorder observed previously in the X‐ray structure of the cis isomer was also reflected in the 13C and 2H MAS spectra. Variable‐temperature 2H MAS spectra of differently deuterated ligand species, that is, the copper(II) complexes with L‐[D2]valine, L‐[D8]valine, and L‐[D10]valine, suggested the dynamic nature of this disorder in the aqua cis isomer and confirmed static ND2 deuterons in the anhydrous trans isomer. Quantum chemical DFT/B3LYP calculations of the 13C hyperfine (Fermi contact) shifts of the paramagnetic term were useful as assignment aids in the interpretation of the 13C MAS spectra.

A Simple and General Method to Determine Reliable Pseudocontact Shifts in Lanthanide Complexes

Pseudocontact shifts (PCS) contain a wealth of geometric information, which makes paramagnetic NMR one of the best methods for accurate geometric determinations in solution. It is well-known that PCS are intrinsically linked to Fermi contact (FC) shifts, and the separation of the two terms is achieved through linearization methods, which heavily rely on (a) isostructurality (even concerning a labile axial site) and (b) the validity of Bleaney's constants. Recently we proposed a method that circumvents both assumptions in the case of axially symmetric complexes, and presently we generalize it to lower symmetry. Our method is model-free and thus does not rely on any structural hypothesis. Our results compare very well with recently published data obtained through an accurate ab initio approach.

Combined NMR Analysis of Huge Residual Dipolar Couplings and Pseudocontact Shifts in Terbium(III)-Phthalocyaninato Single Molecule Magnets

Several small paramagnetic complexes combine large hyperfine NMR shifts with large magnetic anisotropies. The latter are a prerequisite for single molecule magnet (SMM) behavior. We choose the SMM tris(octabutoxyphthalocyaninato) diterbium (1) for a high resolution NMR study where we combined for the first time a comprehensive (1)H and (13)C chemical shift analysis of a SMM with the evaluation of large residual dipolar couplings (RDCs). The latter are a consequence of partial alignment of SMM 1 in the strong magnetic field of the NMR spectrometer. To the best of our knowledge RDCs in SMMs have never been reported before. We measured RDCs between -78 and +99 Hz for the (13)C-(1)H vectors of CH bonds and up to -109 Hz for (1)H-(1)H vectors of geminal hydrogen atoms (magnetic field of 14.09 T, temperature 295 K). Considerable negative Fermi contact shifts (up to -60 ppm) were determined for (13)C atoms at the phthalocyaninato core. Paramagnetic (13)C NMR shifts of the butoxy chains as well as all (1)H NMR chemical shifts are a result of pseudocontact shifts (pcs), and therefore it is easily possible to determine the positions of the respective nuclei in solution. Measurements of CH and HH vectors by RDC analysis are in accordance with the geometry as determined by the pseudocontact shifts, but in addition to that, RDCs give information about internal mobility. The axial component of the magnetic susceptibility tensor has been determined independently by pcs and by RDC.

140 H/D Isotopomers Identified by Long-Range NMR Hyperfine Shifts in Ruthenium(III) Ammine Complexes. Hyperconjugation in Ru–NH3Bonding

(1)H NMR spectra of the paramagnetic cyanide-bridged mixed-valence compound [(η(5)-C5H5)Fe(CO)2(μ-CN)Ru(NH3)5](CF3SO3)3 (I) have been obtained in several solvents. When traces of partially deuterated water are present, instead of a single cyclopentadienyl (Cp) resonance shifted by the hyperfine interaction, numerous well-resolved resonances are observed. The spectra were simulated satisfactorily by giving the appropriate statistical weight to 140 possible H/D isotopomers formed by deuteration in the five ruthenium(III) ammine ligands. The proliferation of distinct resonances occurs because (a) the hyperfine shifts (HSs) due to each sequential deuteration in a single ammine are different and (b) while deuteration in an ammine cis to the cyanide bridge causes a downfield shift, in the trans ammine it causes an upfield shift that is nearly twice as large. All of these shifts exhibit a 1/T dependence, but temperature-independent components, due to large second-order Zeeman effects at the Ru(III) center, are also present. Combining the results of density functional theory calculations with data from metal-metal charge-transfer optical transitions and with the effect of solvent-induced NMR HSs, it is argued that Fermi contact shifts at the Cp protons are insignificant compared to those due to the dipolar (pseudocontact) mechanism. Analytical expressions are presented for the dependence of the HS on the tetragonal component of the ligand field at the Ru(III) ion. The tetragonal field parameter, defined as the energy by which the 4d(xy) orbital exceeds the mean t(2g) orbital energy, was found to be 147, 52, and 76 cm(-1), in dimethylformamide, acetone, and nitromethane, respectively. The effects of deuteration show that there is a significant component of hyperconjugation in the Ru-ammine interaction and that ND3 is a weaker π donor than NH3. A single deuteration in an axial ammine increases the tetragonal field parameter (ν) by +2.8 cm(-1), resulting in a HS of -37 ppb in the Cp proton resonance, whereas a single deuteration in an equatorial ammine decreases the field by -1.5 cm(-1) with a HS of +20 ppb, despite a nominal separation of seven chemical bonds. We analyze the origin of this remarkable sensitivity, which relies on the favorable characteristics of the Ru(III) low-spin t(2g)(5) configuration, having a spin-orbit coupling constant ζ ≈ 950 cm(-1).

Density Functional Theory-Based Bond Pathway Decompositions of Hyperfine Shifts: Equipping Solid-State NMR to Characterize Atomic Environments in Paramagnetic Materials

Solid-state nuclear magnetic resonance (NMR) of paramagnetic samples has the potential to provide a detailed insight into the environments and processes occurring in a wide range of technologically-relevant phases, but the acquisition and interpretation of spectra is typically not straightforward. Structural complexity and/or the occurrence of charge or orbital ordering further compound such difficulties. In response to such challenges, the present article outlines how the total Fermi contact (FC) shifts of NMR observed centers (OCs) may be decomposed into sets of pairwise metal–OC bond pathway contributions via solid-state hybrid density functional theory calculations. A generally applicable “spin flipping” approach is outlined wherein bond pathway contributions are obtained by the reversal of spin moments at selected metal sites. The applications of such pathway contributions in interpreting the NMR spectra of structurally and electronically complex phases are demonstrated in a range of paramagnetic Li-...

A DFT-Based Analysis of the NMR Fermi Contact Shifts in Tavorite-like LiMPO4·OH and MPO4·H2O (M = Fe, Mn, V)

Complementing our work on the experimental measurements and DFT calculations of the NMR Fermi contact shifts for 7Li, 31P, and 1H in the tavorite LiFePO4·OH and homeotypic FePO4·H2O, LiMnPO4·OH, Mn...

Simulation of NMR Fermi Contact Shifts for Lithium Battery Materials: The Need for an Efficient Hybrid Functional Approach

In the context of the development of NMR Fermi contact shift calculations for assisting structural characterization of battery materials, we propose an accurate, efficient, and robust approach based on the use of an all electron method. The full-potential linearized augmented plane wave method, as implemented in the WIEN2k code, is coupled with the use of hybrid functionals for the evaluation of hyperfine field quantities. The WIEN2k code uses an autoadaptive basis set that is highly accurate for the determination of the hyperfine field. Furthermore the implementation of an onsite version for the Hartree–Fock exchange offers the possibility to use hybrid functional schemes at no additional computational cost. In this paper, NMR Fermi contact shifts for lithium are studied in different classes of paramagnetic materials that present an interest in the field of Li-ion batteries: olivine LiMPO4 (M = Mn, Fe, Co, and Ni), anti-NASICON type Li3M2(PO4)3 (M = Fe and V), and antifluorite-type Li6CoO4. Making use of the possibility to apply partial hybrid functionals either only on the magnetic atom or also on the anionic species, we evidence the role played by oxygen atoms on polarization mechanisms. Our method is quite general for an application on various types of materials. Furthermore, it is very competitive compared to the other methods recently proposed that are based either on a plane wave basis set with a PAW implementation or on an LCAO one with a full potential description.

Solid-state NMR analysis of Fe-bearing minerals: implications and applications for Earth sciences

Solid-state nuclear magnetic resonance (NMR) is commonly used in the study of solid structures in Earth sciences; however, it suffers from the impossibility to analyse solid structures containing ferromagnetic particles or paramagnetic elements. We have attempted to decipher the effect of (1) ferromagnetic particles (Fe- Ti-bearing mineral phase) and (2) paramagnetic elements (Fe, Cr, Ni) on the signature of diamagnetic elements ( 1 H, 29 Si, 27 Al) in natural clino- and orthopyroxene from peridotite. The results obtained on these natural minerals have been compared with results obtained for a synthetic mixture of kaolinite + magnetite. The 29 Si, 27 Al Echo-MAS NMR spectra acquired for pyroxenes show signatures that are consistent with previous data. Weak additional anomalous peaks are detected in 29 Si spectra. Both elements show a broadening in the spectra, which is commonly observed when paramagnetic elements are present. The perturbations induced by paramagnetic elements are the result of several interactions: (1) pseudocontact shift and (2) Fermi contact shift. 1 H Echo-MAS NMR spectra for pyroxenes are dramatically affected by the presence of ferromagnetic impurities and are chemical shifted beyond the known range for 1 H in solids. The effect of ferromagnetic particles is also confirmed by the results obtained for the kaolinite + magnetite mixture showing increasing perturbation with increasing magnetite content. We suggest that the presence of paramagnetic elements and/or ferromagnetic particles is only weakly affecting the 29 Si and 27 Al NMR spectra. Thus, new perspectives on the use of NMR technique for mineralogy and geochemistry are envisaged.

Accurate Structure and Dynamics of the Metal-Site of Paramagnetic Metalloproteins from NMR Parameters Using Natural Bond Orbitals

A natural bond orbital (NBO) analysis of unpaired electron spin density in metalloproteins is presented, which allows a fast and robust calculation of paramagnetic NMR parameters. Approximately 90% of the unpaired electron spin density occupies metal–ligand NBOs, allowing the majority of the density to be modeled by only a few NBOs that reflect the chemical bonding environment. We show that the paramagnetic relaxation rate of protons can be calculated accurately using only the metal–ligand NBOs and that these rates are in good agreement with corresponding rates measured experimentally. This holds, in particular, for protons of ligand residues where the point-dipole approximation breaks down. To describe the paramagnetic relaxation of heavy nuclei, also the electron spin density in the local orbitals must be taken into account. Geometric distance restraints for 15N can be derived from the paramagnetic relaxation enhancement and the Fermi contact shift when local NBOs are included in the analysis. Thus, the NBO approach allows us to include experimental paramagnetic NMR parameters of 15N nuclei as restraints in a structure optimization protocol. We performed a molecular dynamics simulation and structure determination of oxidized rubredoxin using the experimentally obtained paramagnetic NMR parameters of 15N. The corresponding structures obtained are in good agreement with the crystal structure of rubredoxin. Thus, the NBO approach allows an accurate description of the geometric structure and the dynamics of metalloproteins, when NMR parameters are available of nuclei in the immediate vicinity of the metal-site.