Search results for "spin coupling"
showing 10 items of 14 documents
From correlation-consistent to polarization-consistent basis sets estimation of NMR spin–spin coupling constant in the B3LYP Kohn–Sham basis set limit
2008
Abstract Based on B3LYP spin–spin coupling constants (SSCC) of several molecules calculated with cc-pV x Z, cc-pCV x Z, cc-pCV x Z-sd and cc-pCV x Z-sd+ t basis sets, a reasonably fit, using the two-parameter formula, to the Kohn–Sham complete basis set limit (CBS) is shown. Improvement in the CBS values going from cc-pV x Z to the most elaborated cc-pCV x Z-sd+ t basis set family is observed: standard deviation for all data drops from 33.7 to 23.1, and from 6.0 to 4.8 Hz after excluding problematic 1 J (F,H) and 1 J (F,C). Calculation of water’s 1 J (OH) using B3LYP/cc-pCV x Z and B3LYP/pcJ- n significantly improved the FC term convergence.
"Through-space" 31P spin-spin couplings in ferrocenyl tetraphosphine coordination complexes: improvement in the determination of the distance depende…
2008
Abstract From the analysis of several nickel and palladium halide complexes of a constrained ferrocenyl tetraphosphine, the existence in solution phase of unique 31P–31P “through-space” nuclear spin–spin coupling constants (JPP) had been previously evidenced. Due to the blocked conformation of the species in solution, and based on the NMR spectra obtained for the complexes and their corresponding solid state X-ray structures, these JPP constants had been shown to clearly depend on the mutual spatial position of the corresponding phosphorus atoms. Herein, the quantitative correlation disclosed at that time (P⋯P distance dependence of coupling constants) is remarkably confirmed, and mathemati…
Quantum phase transitions for an integrable quantum Rabi-like model with two interacting qubits
2022
A two-interacting-qubit quantum Rabi-like model with vanishing transverse fields on the qubit pair is studied. Independently of the coupling regime, this model can be exactly and unitarily reduced to two independent single-spin quantum Rabi models, where the spin-spin coupling plays the role of the transverse field. This transformation and the analytical treatment of the single-spin quantum Rabi model provide the key to prove the integrability of our model. The existence of different first-order quantum phase transitions, characterized by discontinuous two-spin magnetization, mean photon number, and concurrence, is brought to light.
Complete basis set prediction of methanol isotropic nuclear magnetic shieldings and indirect nuclear spin–spin coupling constants (SSCC) using polari…
2009
Efficient B3LYP and BHandH density functionals were used to estimate methanol's nuclear magnetic isotropic shieldings and spin–spin coupling constants in the basis set limit. Polarization‐consistent pcS‐n and pcJ‐n (n = 0, 1, 2, 3 and 4), and segmented contracted XZP, where X = D, T, Q and 5, basis sets were used and the results fitted with simple mathematical formulas. The performance of the methods was assessed from comparison with experiment and higher level calculations. 1J(CH) and 3J(HH) values were determined from very diluted solutions in deuterochloroform and compared with theoretical predictions. The agreement between complete basis set (CBS) density functional theory (DFT) predict…
Through-space spin-spin coupling in acetylenic systems. Ab initio and DFT calculations
2003
Abstract: We have investigated, by means of ab initio and DFT calculations, the magnitude of through-space spin-spin couplings ( J CH and J HH ) in CH/π bonded van der Waals dimers involving acetylene, and in a structurally related covalent compound (4-ethynylphenanthrene). Within regions where the interaction is stabilizing J HH couplings are very small (< 0.1 Hz) for all complexes. In the acetylene-methane complex J CH is also very small, whereas in the acetylene-benzene complex and the acetylene dimer it shows a relatively large dependence on the tilt angle from the T-shaped arrangement, for which the smallest values are calculated, to a parallel slipped arrangement where J CH is ca. 0.5…
On novel magnetic probe for fullerene characterization: Theoretical studies on NMR parameters of free and confined in fullerenes HD and H2 molecules
2015
Chemical characterization and separation of individual fullerenes from a raw reaction mixture need new and efficient tools, including rapid spectroscopic techniques. Recent "molecular surgery" synthesis of endohedral complexes of fullerenes with selected atoms and small molecules has opened a new path for experimental and theoretical studies on structural and spectroscopic properties of these molecular systems. Among them are fullerenes with molecular hydrogen confined within a nanoscale cavity. In this work we report on quantum-chemical prediction of nuclear magnetic shielding (and chemical shift) and indirect spin-spin coupling constant in free HD and H2 molecules, as well as models of co…
Complete basis set B3LYP NMR calculations of CDCl3solvent's water fine spectral details
2008
The assignment of singlet at 1.55 ppm and the 1:1:1 triplet at 1.519 ppm to H2O and HOD in the 400 MHz 1H NMR spectrum of CDCl3 solvent were supported by complete basis set (CBS) GIAO-B3LYP calculated chemical shift and the CBS B3LYP estimated 2J(D,H) spin–spin coupling constant (SSCC). The CBS fitting of B3LYP/cc-pCVxZ and B3LYP/pcJ-n predicted SSCC values, the accurate value of 2J(D,H) = − 1.082 ± 0.030 Hz of HOD in chloroform-d1 and the H/D isotopic shift of 0.0307(1) ppm were reported for the first time. The agreement between CBS B3LYP predicted chemical shift, spin–spin values and experiment was good. Copyright © 2008 John Wiley & Sons, Ltd.
What is the form of muscimol from fly agaric mushroom (Amanita muscaria) in water? An insight from NMR experiment supported by molecular modeling.
2020
ARTYKUŁ Z BADAŃ SPECJALNYCH
Gold(I) Complexes of Ferrocenyl Polyphosphines: Aurophilic Gold Chloride Formation and Phosphine-Concerted Shuttling of a Dinuclear [ClAu···AuCl] Fra…
2016
International audience; A smart steric control of the metallocene backbone in bis- and poly(phosphino)ferrocene ligands favors intramolecular aurophilic interactions between [AuCl] fragments in polynuclear gold(I) complexes. We synthesized and characterized by multinuclear NMR and X-ray diffraction analysis mono-, di-, and polynuclear gold complexes of constrained ferrocenyl diphosphines, which bear either bulky tert-butyl groups or more flexible siloxane substituents at the cyclopentadienyl rings. The complexes meso-1,1'-bis-(diphenylphosphino)-3,3'-di-tert-butylferrocene (4-m), rac-1,1'-bis[bis-(5-methy1-2-furyl)phosphino]-3,3'-di-tert-butyfferrocene (5-r), and rac-1,1'-bis ( diphenylphos…
Prediction of water's isotropic nuclear shieldings and indirect nuclear spin–spin coupling constants (SSCCs) using correlation‐consistent and polariz…
2009
Density functional theory (DFT) was used to estimate water's isotropic nuclear shieldings and indirect nuclear spin-spin coupling constants (SSCCs) in the Kohn-Sham (KS) complete basis set (CBS) limit. Correlation-consistent cc-pVxZ and cc-pCVxZ (x = D, T, Q, 5, and 6), and their modified versions (ccJ-pVxZ, unc-ccJ-pVxZ, and aug-cc-pVTZ-J) and polarization-consistent pc-n and pcJ-n (n = 0, 1, 2, 3, and 4) basis sets were used, and the results fitted with a simple mathematical formula. The performance of over 20 studied density functionals was assessed from comparison with the experiment. The agreement between the CBS DFT-predicted isotropic shieldings, spin-spin values, and the experimenta…