Calculation Of Coupling Constants Research Articles

On the Performance of Second-Order Polarization Propagator Methods in the Calculation of 1JFC and nJFH NMR Spin-Spin Coupling Constants.

This study evaluates the performance of doubles-corrected random phase approximation (RPA) and higher random phase approximation (HRPA) approaches in predicting nuclear magnetic resonance (NMR) coupling constants involving fluorine. Their performance is benchmarked against experimental data and compared with that of higher-level theoretical methods, specifically second-order polarization propagator (SOPPA) and SOPPA(CCSD). Additionally, we discuss their performance relative to density functional theory (DFT). We find that RPA(D) is severely constrained by (near) triplet instabilities, while HRPA(D) demonstrates markedly improved stability. Statistical analysis reveals stronger patterns for carbon-fluorine couplings across the methods and systems investigated compared with fluorine-hydrogen couplings. While SOPPA-based methodologies prove to be superior in accuracy, HRPA(D) shows promising performance in reducing the computational burden of these calculations, albeit with a tendency to underestimate the coupling strength. These findings highlight the potential of HRPA(D) as a practical alternative to SOPPA methods, even for such difficult properties as NMR spin-spin coupling constants involving fluorine, emphasizing its role in improving predictive accuracy and efficiency across diverse chemical environments.

Restricted Open-Shell Cluster Mean-Field theory for Strongly Correlated Systems.

The cluster-based Mean Field method (cMF) and it is second order perturbative correction was introduced by Jiménez-Hoyos and Scuseria to reduce the cost of modeling strongly correlated systems by dividing an active space up into small clusters, which are individually solved in the mean-field presence of each other. In that work, clusters with unpaired electrons are treated by allowing the α and β orbitals to spin polarize. While that provided significant energetic stabilization, the resulting cMF wave function was spin-contaminated, making it difficult to use as a reference state for spin-pure post-cMF methods. In this work, we propose the Restricted Open-shell cMF (RO-cMF) method, extending the cMF approach to systems with open-shell clusters, while not permitting spin-polarization. While the resulting RO-cMF energies are necessarily higher in energy than the unrestricted orbital cMF, the new RO-cMF provides a simple reference state for post-cMF methods that recover the missing intercluster correlations. We provide a detailed explanation of the method, and report demonstrative calculations of exchange coupling constants for three systems: a di-iron complex, a dichromium complex, and a dimerized organic radical. We also report the first perturbatively corrected RO-cMF-PT2 results as well.

Exchange Couplings and Magneto‐Structural Correlations of Trinuclear MII‐UIV‐MII (MII=Co, Ni, Cu) Complexes

AbstractThe magnetic properties of the trinuclear Schiff base complexes M2UL7 (MII=Co, Ni, Cu; L7=N,N’‐bis(3‐hydroxysalicylidene)‐2,2‐dimethyl‐1,3‐propanediamine), exhibiting the [M(μ‐O)2]2U core structure (3d‐5 f‐3d subsystem), have been investigated theoretically using scalar relativistic ZORA/DFT computations combined with the broken symmetry (BS) approach. The calculated coupling constants JMU between the adjacent M1−U and M2−U agree with the observed ferromagnetic (Ferro) character observed in the case of the Cu2UL7 complex, the antiferromagnetic (AF) character of the Ni2UL7 one is consistent with the experimentally observed AF behaviour for Co2UL7. The structural parameters, in particular the M−U distances and the M−Ob−U angles, as well as the electronic factors driving the superexchange couplings are discussed. The bond orders and the magnetic molecular orbital analyses reveal that the U(5 f) covalent contribution to the bonding within the M−O−U coordination is more important in the Co2UL7 and Ni2UL7 complexes than in the Cu2UL7 congener, thus favouring AF coupling between the transition metal and the uranium magnetic centers, in the first complexes. The analyses are supported by the study of the mixed ZnMUL7 and M2ThL7 systems, where the CoII (3d7) and NiII (3d8) paramagnetic ions are replaced by the diamagnetic ZnII(3d10) one, whereas in the second complex, the UIV(5f2) paramagnetic center is replaced by the diamagnetic ThIV(5f0) one. The Natural Populations Analyses confirm the crucial role of spin delocalization that is at work in favour of the AF vs. Ferro magnetic character of the M−U−M (M=Ni, Co) and Cu−U−Cu coordination, respectively.

Simulation and analysis of 13C spin-rotation nuclear magnetic resonance relaxation rates of methyl groups

This work analyzes the nuclear spin–rotation contribution to the nuclear magnetic resonance relaxation of methyl groups from 10 rigid compounds (eight benzene derivatives with one, two, or three methyl groups and two bicyclic molecules) with internal rotation axes not aligned to the smallest molecular moment of inertia via molecular dynamics simulation and ab initio calculation. The molecular dynamics simulation and ab initio calculation of nuclear spin-rotation coupling constants reproduce the experimental behavior in selected systems. The presented methodology can help in the analysis and interpretation of experimental relaxation data.

Calculation of electric field gradients with the exact two-component (X2C) quasi-relativistic method and its local approximations.

When calculating electric field gradients (EFGs), relativistic and electron correlation effects are crucial for obtaining accurate results, and the commonly used density functional methods produce unsatisfactory results, especially for heavy elements and/or strongly correlated systems. In this work, a stand-alone program is presented, which enables calculation of EFGs from the molecular orbitals supplied by an external high accuracy quantum chemical calculation and includes relativistic effects through the exact two-component (X2C) formalism and efficient local approximations to it. Application to BiN and BiP molecules shows that a high precision can be achieved in the calculation of nuclear quadrupole coupling constants of 209Bi by combining advanced ab initio methods with the X2C approach. For seventeen iron compounds, the Mössbauer nuclear quadrupole splittings (NQS) of 57Fe calculated using a double-hybrid functional method are in very good agreement with the experimental values. It is shown that, for strongly correlated molecules, the double-hybrid functionals are much more accurate than the commonly used hybrid functionals. The computer program developed in this study furnishes a useful utility for obtaining EFGs and related nuclear properties with high accuracy.

Tetrabromidocuprate(II) complexes with diprotonated 1-hydroxy-4methyl-2-(pyridin-2-yl)-5-phenylimidazole and 1-hydroxy-2-(pyridin-2-yl)-4,5,6,7-tetrahydrobenzimidazole ligands: Relationship between the structure and magnetic properties

Two new tetrabromidocuprate(II) complexes with diprotonated 1-hydroxy-2-(pyridin-2-yl)-4,5,6,7-tetrahydrobenzimidazole (1) and 1-hydroxy-4methyl-2-(pyridin-2-yl)-5-phenylimidazole (2) were synthesized and their structure established from single-crystal X-ray data. Compounds crystallized in the monoclinic space groups P21/n and P21/c, respectively, where tetrabromidocuprate anions formed magnetic chains as inferred from the distances between the halide ions of different [CuBr4]2− units. Magnetization measurements showed that both compounds behave as well-isolated uniform S = 1/2 antiferromagnetic chains described by the one-dimensional Heisenberg antiferromagnetic model with intra-chain exchange interaction 2 J = 23 K (1) and 2 J = 33 K (2) (the Hamiltonian Hˆ=2J∑SˆiSˆi+1). Electron paramagnetic resonance, optical absorption, and density functional theory investigations provided complementary results for 1 and 2. A calculation of exchange coupling constants gave values of 2 J = 24 K (1) and 2 J = 39 K (2), in good agreement with the experiment. The quantum theory of atoms in molecules and non-covalent interaction analyses showed that halogen bonding determined the exchange interaction between [CuBr4]2− units in magnetic chains of these cation–anion compounds.

Magneto-Structural Analysis of Hydroxido-Bridged CuII2 Complexes: Density Functional Theory and Other Treatments

A selection of dimeric Cu(II) complexes with bidentate N,N′ ligands with the general formula [Cu(L)(X)(μ-OH)]2·nH2O and [Cu(L)(μ-OH)]2X2·nH2O were magneto-structurally analyzed using the Density Functional Theory (DFT). A Broken Symmetry-Density Functional Theory (BS-DFT) study was undertaken for these complexes with relevant decomposition schemes that gave insight into the effect of the nature of the ligand and coordination environment on the DFT-predicted coupling constants (J). The impact of the spin population, which correlates well with the Cu-O-Cu bridging angles and the calculated coupling constant (J) values, was studied. The models were further refined using a complete active space self-consistent field (CASSCF) while expanding the active space from 2 orbitals 2 electrons (2,2) to 10 orbitals 18 electrons (18,10). These models were approximated using multireference methods (n-electron valence state perturbation theory and difference dedicated configuration interaction), and a better approximation of J values was found as expected. Orbitals involved in the superexchange pathway were also visualized.

The Importance of Solvent Effects in Calculations of NMR Coupling Constants at the Doubles Corrected Higher Random-Phase Approximation

In this work, 242 NMR spin–spin coupling constants (SSCC) in 20 molecules are calculated, either with correlated wave function methods, SOPPA and HRPA(D), or with density functional theory based on the B3LYP, BHandH, or PBE0 functionals. The calculations were carried out with and without treatment of solvation via a polarizable continuum model in both the geometry optimization step and/or the SSCC calculation, and thereby, four series of calculations were considered (the full-vacuum calculation, the full-solvent calculation, and the two cross combinations). The results were compared with experimental results measured in a solvent. With the goal of reproducing experimental values, we find that the performance of the PBE0 and BHandH SSCCs improves upon including solvation effects. On the other hand, the quality of the B3LYP SSCCs worsens with the inclusion of solvation. Solvation had almost no effect on the performance of the SOPPA and HRPA(D) calculations. We find that the PBE0-based calculations of the spin–spin coupling constants have the best agreement with the experimental data.

Eta-meson couplings with low-lying nucleon resonances

Using QCD sum rules, supplemented with projected correlation function approach, we have calculated coupling constants of an eta-meson with the two lowest mass nucleon resonances. This includes both the diagonal as well as non-diagonal coupling constants involving a nucleon resonance and a nucleon. For this, we first calculate vacuum-to-eta correlation function of the interpolating fields of two nucleons and then take its matrix elements with respect to a nucleon spinor and/or a nucleon resonance spinor(s). Desired coupling constants are obtained by solving different equations obtained from different matrix elements. Stability of the results with respect to variation of different QCD and phenomenological input parameters has been checked. We have also analyzed the effect of the changes in the coupling constants under the hypothetical situation when the contribution of the hidden strangeness is removed and when that of the anomalous glue is removed from the correlation function.

Isolation and NMR Scaling Factors for the Structure Determination of Lobatolide H, a Flexible Sesquiterpene from Neurolaena lobata

A new flexible germacranolide (1, lobatolide H) was isolated from the aerial parts of Neurolaena lobata. The structure elucidation was performed by classical NMR experiments and DFT NMR calculations. Altogether, 80 theoretical level combinations with existing 13C NMR scaling factors were tested, and the best performing ones were applied on 1. 1H and 13C NMR scaling factors were also developed for two combinations utilizing known exomethylene containing derivatives, and the results were complemented by homonuclear coupling constant (JHH) and TDDFT-ECD calculations to elucidate the stereochemistry of 1. Lobatolide H possessed remarkable antiproliferative activity against human cervical tumor cell lines with different HPV status (SiHa and C33A), induced cell cycle disturbance and exhibited a substantial antimigratory effect in SiHa cells.

Baryon coupling scheme in a unified SU(3) and SU(6) symmetry formalism

We calculate the baryon-meson coupling constants for the spin-1/2 baryonic octet and spin-3/2 decuplet in a unified approach relying on symmetry arguments such as the fact that the Yukawa couplings, present in the Lagrangian density of the Walecka-type models, must be an invariant under SU(3) and SU(6) group transformations. The coupling constants of the baryon with the scalar $\sigma$ meson are fixed to reproduce the known potential depths for the hyperons and $\Delta$ resonances, in an approach that can be extended to all particles. We then apply the calculated coupling constants to study neutron star matter with hyperons and deltas admixed to its composition. We conclude that the $\Delta^-$ is by far the most important exotic particle that can be present in the neutron star interior. It is always present, independent of the chosen parameterization, and might appear in almost every known neutron star, once its onset happens at very low density. Yet, its presence affects the astrophysical properties of the canonical 1.4 M$_\odot$ star, and, in some cases, it can even contribute to an increase in the maximum mass reached.

Integrated Multiscale Multilevel Approach to Open Shell Molecular Systems.

We present a novel multiscale approach to study the electronic structure of open shell molecular systems embedded in an external environment. The method is based on the coupling of multilevel Hartree-Fock (MLHF) and Density Functional Theory (MLDFT), suitably extended to the unrestricted formalism, to Molecular Mechanics (MM) force fields (FF). Within the ML region, the system is divided into active and inactive parts, thus describing the most relevant interactions (electrostatic, polarization, and Pauli repulsion) at the quantum level. The surrounding MM part, which is formulated in terms of nonpolarizable or polarizable FFs, permits a physically consistent treatment of long-range electrostatics and polarization effects. The approach is extended to the calculation of hyperfine coupling constants and applied to selected nitroxyl radicals in an aqueous solution.

Electronic Structure and Magneto-Structural Correlations Study of Cu2UL Trinuclear Schiff Base Complexes: A 3d-5f-3d Case.

The magnetic properties of trinuclear Schiff base complexes M2AnLi (MII = Zn, Cu; AnIV = Th, U; Li = Schiff base; i = 1-4, 6, 7, 9), exhibiting the [M(μ-O)2]2U core structure with adjacent M1···U and M2···U and next-adjacent M1···M2 interactions, featuring 3d-5f-3d subsystems, have been investigated theoretically using relativistic ZORA/B3LYP computations combined with the broken symmetry (BS) approach. Bond order and natural population analyses reveal that the covalent contribution to the bonding within the Cu-O-U coordination is important thus favoring superexchange coupling between the transition metal and the uranium magnetic centers. The calculated coupling constants JCuU between the Cu and U atoms, agree with the observed shift from the antiferromagnetic (AF) character of the L1,2,3,4 complexes to the ferromagnetic (ferro) of the L6,7,9 ones. The structural parameters, i.e., the Cu···U distances and the Cu-O-U angles, as well as the electronic factors driving the magnetic couplings are discussed. The analyses are supported by the study of the mixed ZnCuULi and Cu2ThLi systems, where in the first complex the CuII (3d9) ion is replaced by the diamagnetic ZnII (3d10) one, whereas in the second complex the UIV (5f2) paramagnetic center is replaced by the diamagnetic ThIV (5f0) one.

Searching for the Best Values of NMR Shielding and Spin-Spin Coupling Parameters: CH4-nFn Series of Molecules as the Example.

Attempts at the theoretical interpretation of NMR spectra have a very long and fascinating history. Present quantum chemical calculations of shielding and indirect spin-spin couplings permit modeling NMR spectra when small, isolated molecules are studied. Similar data are also available from NMR experiments if investigations are performed in the gas phase. An interesting set of molecules is formed when a methane molecule is sequentially substituted by fluorine atoms-CH4-nFn, where n = 0, 1, 2, 3, or 4. The small molecules contain up to three magnetic nuclei, each with a one-half spin number. The spectral parameters of CH4-nFn can be easily observed in the gas phase and calculated with high accuracy using the most advanced ab initio methods of quantum chemistry. However, the presence of fluorine atoms makes the calculations of shielding and spin-spin coupling constants extremely demanding. Appropriate experimental 19F NMR parameters are good but also require some further improvements. Therefore, there is a real need for the comparison of existing NMR measurements with available state-of-the-art theoretical results for a better understanding of actual limits in the determination of the best shielding and spin-spin coupling values, and CH4-nFn molecules are used here as the exceptionally important case.

Magnetic ground state of NiCl2/Br2 monolayers encapsulated in UiO-67 MOF, effect of partially filled pores: Ab-initio and Monte Carlo theoretical study

Ab initio calculations are used to study the properties of two dimensional (2D) Transition Metal Halides (TMH, TM=Ni; H = Cl, Br) encapsulated inside a derivative of UiO-67 Metal-Organic Frameworks (MOF). Two monolayers of TMHs (NiCl2 and NiBr2) were isolated from the experimental Crystallographic Information File (CIF) and used in this study. We found that the structure of both monolayers within the MOF (TMH@MOF) have very similar geometries compared to their perfect 2D sheets hypothetically derived from their bulk structures (TMH@bulk) with small distortions in the Metal–Metal (M–M) and Metal–Halide (M–H) bonds. NiCl2 and NiBr2 sheets have a Ferromagnetic (FM) ground state with large intrinsic magnetic moments localized at each metal site. The predicted FM ground state is also confirmed in the magnetic exchange coupling constant (J) calculations between M centers which are found all positive, but non isotropic within each sheet. Weaker interactions with J ≈0.2 meV are found among NN centers in the outer ring compared to J ≈0.85 meV in the inner rings of both monolayers. The calculated Jś are inserted in a Monte Carlo (MC) code to afford Curie temperatures of 27 K and 22 K for NiCl2/Br2 monolayers respectively. Finally, the experimentally collected structures at low metal loading were found to have distinct magnetic properties compared to the completely filled sheets.

QM/MM Simulations for the Broken-Symmetry Catalytic Reaction Mechanism of Human Arginase I.

Human arginase I (HARGI) is a metalloprotein highly expressed in the liver cytosol and catalyzes the hydrolysis of l-arginine to form l-ornithine and urea. Understanding the reaction mechanism would be highly helpful to design new inhibitor molecules for HARGI as it is a target for heart- and blood-related diseases. In this study, we explored the hydrolysis reaction mechanism of HARGI with antiferromagnetic and ferromagnetic coupling between two Mn(II) ions at the catalytic site by employing molecular dynamics simulations coupled with quantum mechanics and molecular mechanics (QM/MM). The spin states, high-spin ferromagnetic couple (SMn1 = 5/2, SMn2 = 5/2), low-spin ferromagnetic couple (SMn1 = 1/2, SMn2 = 1/2), high-spin antiferromagnetic couple (SMn1 = 5/2, SMn2 = −5/2), and low-spin antiferromagnetic couple (SMn1 = 1/2, SMn2 = −1/2) are considered, and the calculated energetics for the complex of the substrate and HARGI are compared. The results show that the high-spin antiferromagnetic couple (SMn1 = 5/2, SMn2 = −5/2) is more stable than other spin states. The low-spin ferromagnetic and antiferromagnetic coupled states are highly unstable compared with the corresponding high-spin states. The high-spin antiferromagnetic couple (SMn1 = 5/2, SMn2 = −5/2) is stabilized by 0.39 kcal/mol compared with the ferromagnetic couple (SMn1 = 5/2, SMn2 = 5/2). The reaction mechanism is independent of spin states; however, the energetics of transition states and intermediates are more stable in the case of the high-spin antiferromagnetic couple (SMn1 = 5/2, SMn2 = −5/2) than the corresponding ferromagnetic state. It is evident that the calculated coupling constants are higher for antiferromagnetic states and, interestingly, superexchange coupling is found to occur between Mn(II) ions via hydroxide ions in a reactant. The hydroxide ion enhances the coupling interaction and initiates the catalytic reaction. It is also noted that the first intermediate structure where there is no superexchange coupling is similar to the known inhibitor 2(S)-amino-6-boronohexanoic acid.

Pion couplings with low-lying nucleon resonances

We have calculated coupling constants of a neutral pion with the lowest two nucleon resonances. This includes both the diagonal as well as non-diagonal coupling constants involving a nucleon resonance and a nucleon. For this, we first calculate vacuum-to-pion correlation function of the interpolating fields of two nucleons and then take its matrix elements with respect to a nucleon spinor and/or a nucleon resonance spinor(s). Using different QCD sum rules obtained from different matrix elements we eliminate unwanted coupling constants and solve for the desired ones. This is a simple extension of the projected correlation function approach used in the literature where we use multiple of states involving those of a nucleon and its resonances. We have also checked the stability of our results with respect to variation of different QCD and phenomenological input parameters.

Central exclusive production of axial-vector f1 mesons in proton-proton collisions within the tensor-pomeron approach

We discuss the central exclusive production of f_{1}f1 mesons in proton-proton collisions. The diffractive pomeron-pomeron fusion process within the tensor-pomeron approach is considered. Two ways to construct the pomeron-pomeron-f_{1}f1 coupling are discussed. The theoretical calculation of coupling constants is a challenging problem of nonperturbative QCD. We adjust the parameters of the model to the WA102 experimental data. The total cross section and differential distributions are presented. Predictions for LHC experiments are given. Detailed analysis of the distributions in \phi_{pp}ϕpp the azimuthal angle between the transverse momenta of the outgoing protons can help to check different models and to study real pattern of the absorption effects.

Strangeness content of the pion in the U(3) Nambu–Jona–Lasinio model

Abstract The Nambu–Jona–Lasinio model is considered with flavor-dependent coupling constants G i j ( ψ ¯ λ i ψ ) ( ψ ¯ λ j ψ ) + ( ψ ¯ i γ 5 λ i ψ ) ( ψ ¯ i γ 5 λ j ψ ) for i , j = 0 , 1 … N f 2 − 1 , and N f = 3. A self-consistent calculation of quark effective masses and coupling constants is performed, making the strange quark effective mass vary considerably. Quantum mechanical mixings between up, down and strange constituent quarks yield a strangeness content (s-content) of the light u and d quark constituent and of the pion. Different types of estimates for the strangeness contribution for the pion mass are provided. Mixing-type interactions, G i≠j , induce light meson mixings, and estimates for the π 0 − η and η − η′ mixings are provided. The η − π 0 mixing is argued to be an indication of the s-content of the pion.

Study of Self-Interaction Errors in Density Functional Calculations of Magnetic Exchange Coupling Constants Using Three Self-Interaction Correction Methods.

We examine the role of self-interaction error (SIE) removal on the evaluation of magnetic exchange coupling constants. In particular, we analyze the effect of scaling down the self-interaction correction (SIC) for three nonempirical density functional approximations (DFAs) namely, the local spin density approximation, the Perdew-Burke-Ernzerhof generalized gradient approximation, and the recent SCAN family of meta-GGA functionals. To this end, we employ three one-electron SIC methods: Perdew-Zunger SIC [Perdew, J. P.; Zunger, A. Phys. Rev. B, 1981, 23, 5048.], the orbitalwise scaled SIC method [Vydrov, O. A. et al. J. Chem. Phys. 2006, 124, 094108.], and the recent local scaling method [Zope, R. R. et al. J. Chem. Phys. 2019, 151, 214108.]. We compute the magnetic exchange coupling constants using the spin projection and nonprojection approaches for sets of molecules composed of dinuclear and polynuclear H···He models, organic radical molecules, and chlorocuprate and compare these results against accurate theories and experiment. Our results show that for the systems that mainly consist of single-electron regions, PZSIC performs well, but for more complex organic systems and the chlorocuprates, an overcorrecting tendency of PZSIC combined with the DFAs utilized in this work is more pronounced, and in such cases, LSIC with kinetic energy density ratio performs better than PZSIC. Analysis of the results in terms of SIC corrections to the density and to the total energy shows that both density and energy correction are required to obtain an improved prediction of magnetic exchange couplings.