The nuclear electric quadrupole moment of copper

Santiago, Régis T.; Teodoro, Tiago Quevedo; Haiduke, Roberto Luiz Andrade

doi:10.1039/c4cp00706a

Cited by 13 publications

(33 citation statements)

References 49 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Calculated copper C Q values reported here were adjusted to incorporate the more recent value of −19.8 fm 2 for Q( 63 Cu). 10 4 ] + ) = 1193.7 and 1099.5 ppm, respectively, for calculations with the 6-31+G* and 6-311+G* basis sets). The structure for [Cu(NCCH 3 ) 4 ] + is based on that determined by X-ray crystallography by Zhu and co-workers, 61 although in our case average bond length values were used, and tetrahedral symmetry about the copper atom was assumed.…”

Section: Articlementioning

confidence: 99%

Solid-State ⁶³Cu, ⁶⁵Cu, and ³¹P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes

Tan

Bernard

et al. 2015

J. Phys. Chem. A

View full text Add to dashboard Cite

The results of a solid-state (63/65)Cu and (31)P NMR investigation of several copper(I) complexes with functionalized 3-(2'-pyridyl)-1,2,4-triazole and phosphine ligands that have shown potential in the preparation of photoluminescent devices are reported. For each complex studied, distinct NMR parameters, with moderate (63)Cu nuclear quadrupolar coupling constant (CQ) values ranging from -17.2 to -23.7 MHz, are attributed to subtle variations in the distorted four-coordinate environments about the copper nuclei. The spans of the copper chemical shift (CS) tensors, δ11-δ33, for the mono- and bisphosphine complexes are also similar, ranging from 1000 to 1150 ppm, but that for a complex with a strained bidentate phosphine ligand is only 650 ppm. The effects of residual dipolar and indirect spin-spin coupling arising from the (63/65)Cu- (31)P spin pairs, observed in the solid-state (31)P NMR spectra of these complexes, yield information about the orientations of the copper electric field gradient (EFG) tensors relative to the Cu-P bond. Variable-temperature (31)P NMR measurements for [Cu(bptzH)(dppe)]ClO4 (bptzH = 5-tert-butyl-3-(2'-pyridyl)-1,2,4-triazole; dppe = 1,2-bis(diphenylphosphino)ethane), undertaken to investigate the cause of the broad unresolved spectra observed at room temperature, demonstrate that the broadening arises from partial self-decoupling of the (63/65)Cu nuclei, a consequence of rapid quadrupolar relaxation. Ab initio calculations of copper EFG and CS tensors were performed to probe relationships between NMR parameters and molecular structure. The analysis demonstrated that CQ((63/65)Cu) is negative for all complexes studied here and that the largest components of the EFG tensors are generally coincident with δ11.

show abstract

Section: Articlementioning

confidence: 99%

Solid-State ⁶³Cu, ⁶⁵Cu, and ³¹P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes

Tan

Bernard

et al. 2015

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…Moreover, tighter p Gaussians than the ones mentioned here are not considered because they lead to numerical oscillations in analytical EFG values that are probably associated with small imprecisions in coefficients for these functions in deep core spinors. In addition, as presented in Table III, However, those p and d Gaussian functions with the largest exponents may also be the cause of significant inaccuracies in the electron correlation contributions derived from the twopoint numerical approach [28]. Thus, a comparison of the analytical and finite difference DC-HF values obtained for the EFG at gold in AuH indicated that the four tightest p and d functions must be removed from the basis of this element to provide stable numerical results.…”

Section: A Gold Basis Set Incrementmentioning

confidence: 93%

“…This step is carried out with DC-HF and DC-B3LYP calculations for AuH, following a strategy outlined in our previous studies [28]. We noticed in Table III that some tighter functions are required since they cause EFG variations of at least 0.002 a.u.…”

Section: A Gold Basis Set Incrementmentioning

confidence: 99%

See 1 more Smart Citation

Nuclear electric quadrupole moment of gold from the molecular method

Santiago

Haiduke

2015

Phys. Rev. A

Self Cite

View full text Add to dashboard Cite

The nuclear electric quadrupole moment (NQM) of gold is reviewed by means of the molecular method and data from as many as 15 linear systems. The electric-field gradients (EFGs) used to this end were obtained with the Dirac-Coulomb Hamiltonian and coupled-cluster theory, CCSD(T) and CCSD-T, by means of an augmented relativistic basis set for gold. The direct approach was found to be inadequate for the diatomic molecules investigated, which is probably due to improper treatment of the static electron correlation. However, these effects are much less relevant for OCAuX (X = F, Cl, Br, and I) complexes. Thus, the indirect version of the molecular method is preferred in this case. Hence, a NQM value of 515(15) mb is determined for 197Au from linear regressions performed with the best EFGs determined for ten of these systems.

show abstract

“…This analysis reinforced the conclusion that functionals available nowadays are not capable of providing a satisfactory description of these EFGs, which has been customarily pointed out in the literature. [5,14,33] . Another study from the literature that considered first-row transition metal nuclei also concluded that PBE0 is one of the best choices for such EFG calculations.…”

Section: Evaluation and Reparameterization Of Density Functionalsmentioning

confidence: 99%

New density functional parameterizations to accurate calculations of electric field gradient variations among compounds

Santiago¹,

Haiduke²

2015

J Comput Chem

Self Cite

View full text Add to dashboard Cite

This research provides a performance investigation of density functional theory and also proposes new functional parameterizations to deal with electric field gradient (EFG) calculations at nuclear positions. The entire procedure is conducted within the four-component formalism. First, we noticed that traditional hybrid and long-range corrected functionals are more efficient in the description of EFG variations for a set of elements (indium, antimony, iodine, lutetium, and hafnium) among linear molecules. Thus, we selected the PBE0, B3LYP, and CAM-B3LYP functionals and promoted a reoptimization of their parameters for a better description of these EFG changes. The PBE0q variant developed here showed an overall promising performance in a validation test conducted with potassium, iodine, copper, and gold. In general, the correlation coefficients found in linear regressions between experimental nuclear quadrupole coupling constants and calculated EFGs are improved while the systematic EFG errors also decrease as a result of this reparameterization.

show abstract

The nuclear electric quadrupole moment of copper

Cited by 13 publications

References 49 publications

Solid-State ⁶³Cu, ⁶⁵Cu, and ³¹P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes

Solid-State ⁶³Cu, ⁶⁵Cu, and ³¹P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes

Nuclear electric quadrupole moment of gold from the molecular method

New density functional parameterizations to accurate calculations of electric field gradient variations among compounds

Contact Info

Product

Resources

About

The nuclear electric quadrupole moment of copper

Cited by 13 publications

References 49 publications

Solid-State 63Cu, 65Cu, and 31P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes

Solid-State 63Cu, 65Cu, and 31P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes

Nuclear electric quadrupole moment of gold from the molecular method

New density functional parameterizations to accurate calculations of electric field gradient variations among compounds

Contact Info

Product

Resources

About

Solid-State ⁶³Cu, ⁶⁵Cu, and ³¹P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes

Solid-State ⁶³Cu, ⁶⁵Cu, and ³¹P NMR Spectroscopy of Photoluminescent Copper(I) Triazole Phosphine Complexes