Nuclear Magnetic Shielding Constants Research Articles

Caffeine-Legal Natural Stimulant with Open Research Perspective: Spectroscopic and Theoretical Characterization.

Caffeine is an alkaloid with a purine structure and has been well known for centuries due to its presence in popular drinks-tea and coffee. However, the structural and spectroscopic parameters of this compound, as well as its chemical and biological activities, are still not fully known. In this study, for the first time, we report on the measured oxygen-17 NMR spectra of this stimulant. To support the assignment of our experimental NMR data, extensive quantum chemical calculations of NMR parameters, including nuclear magnetic shielding constants and indirect spin-spin coupling constants, were performed. In a theoretical study, using nine efficient density functionals (B3LYP, BLYP, BP86, CAM-B3LYP, LC-BLYP, M06, PBE0, TPSSh, wB97x), and in combination with a large and flexible correlation-consistent aug-cc-pVTZ basis set, the structure and NMR parameters were predicted for a free molecule of caffeine and in chloroform, DMSO and water. A polarized continuum model (PCM) was used to include a solvent effect. As a result, an optimal methodology was developed for predicting reliable NMR data, suitable for studies of known, as well as newly discovered, purines and similar alkaloids. The results of the current work could be used in future basic and applied studies, including NMR identification and intermolecular interactions of caffeine in various raw materials, like plants and food, as well as in the structural and spectroscopic characterization of new compounds with similar structures.

Efficiently Computing NMR 1H and 13C Chemical Shifts of Saccharides in Aqueous Environment.

Determining the structure of saccharides in their native environment is crucial to understanding their function and more accurately targeting their utilization. Nuclear magnetic resonance observables such as the nuclear Overhauser effect or spin-spin coupling constants are routinely utilized to study saccharides in their native water environment. However, while highly sensitive to the local environment, chemical shifts are mostly overlooked, despite being commonly measured for compounds identification. Although chemical shifts carry considerable structural information, their direct association with structure is notoriously difficult. This is mostly due to the similarity in the chemical nature of most saccharides causing similar physicochemical environments close to sugar C and H atoms, resulting in comparable chemical shifts. The rise of computational power allows one to compute reliable chemical shifts and use them to determine atomistic details of these sugars in solution. However, any prediction is severely limited by the computational protocol used and its accuracy. In this work, we studied a set of 31 saccharides on which we evaluated various computational protocols to calculate the total number of 375 1H and 327 13C chemical shifts of sugars in an aqueous environment. Our study proposes two cost-effective protocols for simulating 1H and 13C chemical shifts that we recommend for further use. These protocols can help with the interpretation of experimental spectra, but we also show that they are also capable of structure prediction independently. This is possible because of the low mean absolute deviations of calculated shifts from the experiment (0.06 ppm for 1H and 1.09 ppm for 13C). We explore different solvation methods, basis sets, and optimization schemes to reach such accuracy. A correct sampling of the conformation phase space of flexible sugar molecules is also key to obtaining accurately converged theoretical chemical shifts. The linear regression method was applied to convert the calculated isotropic nuclear magnetic shielding constants to simulated chemical shifts comparable with the experiment. The achieved level of accuracy can help in utilizing chemical shifts for elucidating the 3D atomistic structure of saccharides in aqueous solutions. All linear regression parameters obtained on our extensive set of sugars for all the tested protocols can be reutilized in future works.

Probing Nuclear Dipole Moments and Magnetic Shielding Constants through 3-Helium NMR Spectroscopy

Multinuclear NMR studies of the gaseous mixtures that involve volatile compounds and 3He atoms are featured in this review. The precise analyses of 3He and other nuclei resonance frequencies show linear dependencies on gas density. Extrapolation of the gas phase results to the zero-pressure limit gives the ν0(3He) and ν0(nX) resonance frequencies of nuclei in a single 3-helium atom and nuclei in molecules at a given temperature. The NMR frequency comparison method provides an approach for determining different nuclear magnetic moments. The application of quantum chemical shielding calculations, which include a more complete and careful theoretical treatment, allows the shielding of isolated molecules to be achieved with great accuracy and precision. They are used for the evaluation of nuclear moments, without shielding impacts on the bare nuclei, for: 10/11B, 13C, 14N, 17O, 19F, 21Ne, 29Si, 31P, 33S, 35/37Cl, 33S, 83Kr, 129/131Xe, and 183W. On the other hand, new results of nuclear moments were used for the reevaluation of absolute nuclear magnetic shielding in the molecules under study. Additionally, 3He gas in water solutions of lithium and sodium salts was used for measuring 6/7Li and 23Na magnetic moments and reevaluating the shielding parameters of Li+ and Na+ water-solvated cations. In this paper, guest 3He atoms that play a role in probing the electron density in many host macromolecules are also presented.

Theoretical Study of the Isotope and Homologue Effects on Nuclear Magnetic Shielding in Water and Hydrogen Sulfide Molecules

Abstract The hydrogen/deuterium isotope and oxygen/sulfur homologue effects on the absolute nuclear magnetic shielding constants were theoretically analyzed for five 17O-water isotopologues and five hydrogen sulfide isotopologues. Using both ab initio calculations and anharmonic vibrational structure calculations based on vibrational quantum Monte Carlo theory, we confirmed that the changes in the atomic charges are strongly correlated with the enhancements of the absolute nuclear magnetic shielding constants.

Spatial Contributions to 1H NMR Chemical Shifts of Free-Base Porphyrinoids

A recently developed methodology for calculating, analyzing, and visualizing nuclear magnetic shielding densities is used for studying spatial contributions including ring-current contributions to 1H nuclear magnetic resonance (NMR) chemical shifts of aromatic and anti-aromatic free-base porphyrinoids. Our approach allows a visual inspection of the spatial origin of the positive (shielding) and negative (deshielding) contributions to the nuclear magnetic shielding constants. Diatropic and paratropic current-density fluxes yield both shielding and deshielding contributions implying that not merely the tropicity of the current density determines whether the contribution has a shielding or deshielding character. Instead the shielding or deshielding contribution is determined by the direction of the current-density flux with respect to the studied nucleus.

A study of some atomic properties for He-like selected ions

The atomic properties have been studied for He-like ions (He atom, Li+, Be2+ and B3+ions). These properties included, the atomic form factor f(S), electron density at the nucleus , nuclear magnetic shielding constant and diamagnetic susceptibility ,which are very important in the study of physical properties of the atoms and ions. For these purpose two types of the wave functions applied are used, the Hartree-Fock (HF) waves function (uncorrelated) and the Configuration interaction (CI) wave function (correlated). All the results and the behaviors obtained in this work have been discussed, interpreted and compared with those previously obtained.

Spatial Contributions to Nuclear Magnetic Shieldings.

We develop a methodology for calculating, analyzing, and visualizing nuclear magnetic shielding densities which are calculated from the current density via the Biot–Savart relation. Atomic contributions to nuclear magnetic shielding constants can be estimated within our framework with a Becke partitioning scheme. The new features have been implemented in the GIMIC program and are applied in this work to the study of the 1H and 13C nuclear magnetic shieldings in benzene (C6H6) and cyclobutadiene (C4H4). The new methodology allows a visual inspection of the spatial origins of the positive (shielding) and negative (deshielding) contributions to the nuclear magnetic shielding constant of a single nucleus, something which has not been hitherto easily accomplished. Analysis of the shielding densities shows that diatropic and paratropic current-density fluxes yield both shielding and deshielding contributions, as the shielding or deshielding is determined by the direction of the current-density flux with respect to the studied nucleus instead of the tropicity. Becke partitioning of the magnetic shieldings shows that the magnetic shielding contributions mainly originate from the studied atom and its nearest neighbors, confirming the localized character of nuclear magnetic shieldings.

Ядерное магнитное экранирование в многозарядных ионах

The nuclear magnetic shielding is considered within the fully relativistic approach for the ground state of H-, Li-, and B-like ions in the range Z=32-92. The interelectronic interaction is evaluated to the first order of the perturbation theory in Li- and B-like ions. The calculations are based on the finite-field method. The numerical solution of the Dirac equation with the magnetic-field and hyperfine interactions included within the dual-kinetic-balance method is employed. The nuclear magnetic shielding constant is an important ingredient for accurate determination of the nuclear magnetic moments from the high-precision g-factor measurements.

Conformational and electronic study of dopamine interacting with the D2 dopamine receptor.

We report an exhaustive conformational and electronic study on dopamine (DA) interacting with the D2 dopamine receptor (D2 DR). For the first time, the complete surface of the conformational potential energy of the complex DA/D2 DR is reported. Such a surface was obtained through the use of QM/MM calculations. A detailed study of the molecular interactions that stabilize and destabilize the different molecular complexes was carried out using two techniques: Quantum Theory of Atoms in Molecules computations and nuclear magnetic shielding constants calculations. A comparative study of the behavior of DA in the gas phase, aqueous solution, and in the active site of D2 DR has allowed us to evaluate the degree of deformation suffered by the ligand and, therefore, analyze how rustic are the lock-key model and the induced fit theory in this case. Our results allow us to propose one of the conformations obtained as the "biologically relevant" conformation of DA when it is interacting with the D2 DR.

Performance of the LRESC Model on top of DFT Functionals for Relativistic NMR Shielding Calculations.

The linear response within the elimination of the small component model (LRESC) is an insightful and computationally efficient method for including relativistic effects on molecular properties like the nuclear magnetic shielding constants, spin-rotation constant, g-tensor, and electric field gradient of heavy atom containing molecules with atoms belonging up to the sixth row of the periodic table. One of its main advantages is its capacity to analyze the electronic origin of the different relativistic correcting terms. Until now, it was always applied on top of Hartree-Fock ground-state wave functions (LRESC/HF) to calculate and analyze NMR shieldings. In this work, we show the performance of the LRESC formalism on top of some density functional theory (DFT) functionals to compute tin shielding constants in SnX4 (X = H, F, Cl, Br, I) molecular systems. We analyze the performance of each LRESC/DFT scheme on reproducing the electronic mechanisms of the shieldings, taking as a benchmark the results of relativistic calculations at the RPA level of approach (4c/RPA). As in previous works, we divide the LRESC relativistic correcting terms into two groups: core-dependent and ligand-dependent contributions. It is shown here that core-dependent corrections are well-reproduced for the selected DFT functionals, but some differences arise in the ligand-dependent ones. We focus on the performance of different functionals, including the same electron correlation part but containing different amounts of HF exchange. The best results are obtained for the BHandHLYP functional (50% of HF exchange) and the worst for BLYP (0%). When the percentage of HF exchange increases, ligand-dependent contributions are better described, and the final LRESC/DFT results are closer to those obtained with LRESC/HF and 4c/RPA methods. The spin-orbit correction to the shielding constant is one of the main ligand-dependent contributions (there are two more) with total value depending on the amount of HF exchange included in the functional. When the amount of HF exchange decreases, the spin-orbit contribution becomes larger, overestimating the shielding constant even when nonrelativisitc DFT values are much smaller than the nonrelativistic HF ones, as it happens for the heaviest molecular system studied here (SnI4).

The 13C nuclear magnetic shielding constants at the singlet excited states in CH2CCH2, CH2O, CH3CHO, CH3NH2, and CO

Abstract Quantum-chemical calculations of excited state nuclear shielding constants are reported for singlet states in CH2CCH2, CH2O, CH3CHO, CH3NH2, and CO. The multiconfigurational self-consistent field method is used to account for static correlation in the excited states. With one exception, the molecules considered had larger shielding constants in their excited states than in their ground states. This tendency towards deshielding is rationalized using the sum-over-states expression for magnetic response.

Method Calibration or Data Fitting?

We investigate by explicit parameter optimization to what extent basis sets of polarized double-ζ quality can introduce compensating errors in five different density functional methods. It is shown that minor changes in the contraction coefficients of the valence functions in the basis sets can have a significant impact and allow different density functional methods to achieve very similar performances. This holds for nuclear magnetic shielding constants and for isomerization energies, barrier heights, and noncovalent interactions. It is furthermore shown that errors due to neglect of vibrational and solvent effects can be absorbed in the combined method and basis set errors. These findings hold for data sets consisting of 50-150 data points. This raises the question of whether the common practice of identifying combinations of density functional methods and basis sets that have a good performance against a selected set of reference data should be considered as data fitting in the combined parameter space spanned by the method and basis set.

Gauge-origin independent formalism of two-component relativistic framework based on unitary transformation in nuclear magnetic shielding constant.

This article proposes a gauge-origin independent formalism of the nuclear magnetic shielding constant in the two-component relativistic framework based on the unitary transformation. The proposed scheme introduces the gauge factor and the unitary transformation into the atomic orbitals. The two-component relativistic equation is formulated by block-diagonalizing the Dirac Hamiltonian together with gauge factors. This formulation is available for arbitrary relativistic unitary transformations. Then, the infinite-order Douglas-Kroll-Hess (IODKH) transformation is applied to the present formulation. Next, the analytical derivatives of the IODKH Hamiltonian for the evaluation of the nuclear magnetic shielding constant are derived. Results obtained from the numerical assessments demonstrate that the present formulation removes the gauge-origin dependence completely. Furthermore, the formulation with the IODKH transformation gives results that are close to those in four-component and other two-component relativistic schemes.

Convergence of nuclear magnetic shieldings and one-bond 1 J(11 B1 H) indirect spin-spin coupling constants in small boron molecules.

Self-consistent field Hartree-Fock, density functional theory, and coupled-cluster calculations of the nuclear magnetic shielding constants of BH and BH3 molecules have been conducted to characterize the convergence of individual results obtained with correlation-consistent and polarization-consistent basis sets. The individual 11 B and 1 H NMR parameters were estimated in the complete basis set limit and compared with benchmark results. Only the KT3 density functional accurately reproduced 11 B shielding in BH molecule.

Self-Consistent Field Calculation of Nuclear Magnetic Resonance Chemical Shielding Constants Using Gauge-Including Atomic Orbitals and Approximate Two-Electron Integrals.

The chain-of-spheres method (COS) for approximating two-electron integrals is applied to Hartree-Fock and density functional theory calculations of nuclear magnetic resonance chemical shielding tensors, based on gauge-including atomic orbitals. The accuracy of the approximation is compared to that of the resolution of the identity (RI) approach, using a benchmark test set of 15 small molecules. Reasonable auxiliary basis sets and grid sizes are selected on the basis of a careful investigation of how approximating each of the two-electron terms in the self-consistent field (SCF) and coupled perturbed SCF equations affects the calculated shielding constants. It is found that the errors are linearly additive but can have either sign. The mean absolute relative error due to applying the RI/COS approximations with the chosen settings to all two-electron terms is on the order of 0.01% and therefore negligible compared to the errors due to basis set incompleteness (∼1%) and the method used (10-50%). Several larger organic systems are used to assess the efficiency of the RI approximation for both Coulomb- and exchange-type integrals (RIJK) as well as a combination of RI for Coulomb and COS for exchange contributions (RIJCOSX). The RIJK approximation is more efficient for small molecules, while for systems of over 100 electrons and 1000 basis functions, the RIJCOSX approximation is superior.

Calculations of nuclear magnetic shielding constants based on the exact two-component relativistic method.

From the matrix representation of the modified Dirac equation based on the restricted magnetically balanced gauge-including atomic orbital (RMB-GIAO) basis, previously one of the authors (Yoshizawa) and co-workers derived the two-component normalized elimination of the small component (2c-NESC) formulas for 2c relativistic calculations of nuclear magnetic resonance (NMR) shielding tensors. In the present study, at the Hartree-Fock (HF) level, we numerically confirm that for several molecules the RMB-GIAO-based 2c-NESC method provides gauge-origin independent NMR shielding values. Moreover, we investigate the accuracy of the 2c-NESC method by comparison with the 4c relativistic NMR calculations at the HF level. For noble gas dimers and Hg compounds, it is shown that the 2c-NESC method reproduces the 4c relativistic NMR shielding constants within errors of 0.12%-0.31% of the 4c relativistic values and yields chemical shifts sufficiently close to the 4c relativistic results. Also, we discuss the basis set convergence of NMR shielding constants calculated with the 2c-NESC and 4c relativistic methods.

Quantum chemical investigations on hydrogen bonding interactions established in the inclusion complex β-cyclodextrin/benzocaine through the DFT, AIM and NBO approaches

Structure and stability of an inclusion complex formed by Benzocaine (BZC) and β-cyclodextrin (β-CD) were investigated computationally using different levels of theory. The conformational research based on PM6 method allowed reach two minimum-energy structures: model A and model B. The lowest conformers have been exposed to fully geometry optimization employing four DFT functionals: B3LYP, CAM-B3LYP, M05-2X and M06-2X. The performed DFT calculations have identified the model B, in which the amino group is located at the primary face of β-CD, as the most stable complex by an amount up to −40 kcal/mol. Further, the greater stabilization of model B in respect to model A, has been ascertained through AIM and NBO analyses which clarified the main hydrogen bonds HBs interactions governing the reactivity of BZC inside the hydrophobic cavity of β-CD. Finally, the estimated isotropic 1H nuclear magnetic shielding constants generated from the gauge-including-atomic-orbital calculation have been analyzed and then compared with the available experimental data.

Nuclear magnetic shielding constants of Dirac one-electron atoms in some low-lying discrete energy eigenstates

We present tabulated data for the nuclear magnetic shielding constants (σ) of the Dirac one-electron atoms with a pointlike, motionless and spinless nucleus of charge Ze. Utilizing the exact general analytical formula for σ derived by us (Stefańska, 2016) valid for an arbitrary discrete energy eigenstate, we have computed the numerical values of the magnetic shielding factors for the ground state and for the first and the second set of excited states, i.e.: 2s1∕2, 2p1∕2, 2p3∕2, 3s1∕2, 3p1∕2, 3p3∕2, 3d3∕2, and 3d5∕2, of the relativistic hydrogenic ions with the nuclear charge numbers from the range 1⩽Z⩽137. The comparisons of our results with the numerical values reported by other authors for some atomic states are also presented.

The hyperfine structure in the rotational spectra of D2(17)O and HD(17)O: Confirmation of the absolute nuclear magnetic shielding scale for oxygen.

Guided by theoretical predictions, the hyperfine structures of the rotational spectra of mono- and bideuterated-water containing (17)O have been experimentally investigated. To reach sub-Doppler resolution, required to resolve the hyperfine structure due to deuterium quadrupole coupling as well as to spin-rotation (SR) and dipolar spin-spin couplings, the Lamb-dip technique has been employed. The experimental investigation and in particular, the spectral analysis have been supported by high-level quantum-chemical computations employing coupled-cluster techniques and, for the first time, a complete experimental determination of the hyperfine parameters involved was possible. The experimentally determined (17)O spin-rotation constants of D2 (17)O and HD(17)O were used to derive the paramagnetic part of the corresponding nuclear magnetic shielding constants. Together with the computed diamagnetic contributions as well as the vibrational and temperature corrections, the latter constants have been employed to confirm the oxygen nuclear magnetic shielding scale, recently established on the basis of spin-rotation data for H2 (17)O [Puzzarini et al., J. Chem. Phys. 131, 234304 (2009)].

GIAO Calculations of Chemical Shifts of NMR Spectra of 1H and 13C of the Hexahydroindoles Products

Isotropic 1 H and 13 C nuclear magnetic shielding constants of hexahydroindoles products of intramolecular Diels-Alder of the triene-amide reaction have been calculated by employing the gauge-including-atomic-orbital (GIAO), Continuous Set of Gauge Transformations (CSGT) and a slight variation on the CSGT (IGAIM) methods at the B3LYP/6-311(d,p) density functional level of theory. Geometry of each compound has been optimized employing 6-31G(d,p) basis sets. The comparison of the theoretical results to the experimental results of the Ha compound shows that the GIAO method is the most reliable. On the other hand we calculate the chemicals shifts of the carbon ( 13 C) and hydrogen ( 1 H) of the Hb and Hc compounds. This calculation was performed using the B3LYP functional, using the GIAO method at the level of the following bases: 6-31G, 6-31 G(d), 6-31G(d,p), 6-311G, 6-311G(d). The theoretical trends are compared with experimental data taken from the literature. The least squares regression analyses of the results indicate R-square values greater than 0.90 in the range for total data set.