Substituent Effects on Scalar2J(19F,19F) and3J(19F,19F) NMR Couplings:  A Comparison of SOPPA and DFT Methods

Barone, Verónica; Provasi, Patricio F.; Peralta, Juan E.; Snyder, James P.; Sauer, Stephan P. A.; Contreras, Rubén H.

doi:10.1021/jp0300851

Cited by 104 publications

(89 citation statements)

References 48 publications

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“…PSO and SD, terms, which dominate the total coupling. This behavior is quite typical for couplings between atoms with more than one lone-pair 135,160,172, 215,216,244,245 . The PSO term is thus the largest contribution in ClF and is more than six times as large as the FC term.…”

Section: B Differences Between Hydrides and Fluoridesmentioning

confidence: 88%

Optimized basis sets for the calculation of indirect nuclear spin-spin coupling constants involving the atoms B, Al, Si, P, and Cl

Provasi

Sauer

2010

The Journal of Chemical Physics

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The aug-cc-pVTZ-J series of basis sets for indirect nuclear spin-spin coupling constants has been extended to the atoms B, Al, Si, P and Cl. The basis sets were obtained according to the scheme previously described by Provasi et al. [J. Chem. Phys 115, 1324-1334]. First the completely uncontracted correlation consistent aug-cc-pVTZ basis sets were extended with four tight s and three tight d functions.Secondly the s and p basis functions were contracted with the molecular orbital coefficients of self-consistent-field calculations performed with the uncontracted basis sets on the simplest hydrides of each atom. As a first illustration we have calculated the one-bond indirect spin-spin coupling constants in BH − 4 , BF, AlH, AlF, SiH 4 , SiF 4 , PH 3 , PF 3 , H 2 S, SF 6 , HCl and ClF at the level of density functional theory using the Becke three parameter Lee-Yang-Parr (B3LYP), and the second order polarization propagator approximation with coupled cluster singles and doubles amplitudes -SOPPA(CCSD).

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Section: B Differences Between Hydrides and Fluoridesmentioning

confidence: 88%

Optimized basis sets for the calculation of indirect nuclear spin-spin coupling constants involving the atoms B, Al, Si, P, and Cl

Provasi

Sauer

2010

The Journal of Chemical Physics

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“…These last mechanisms are related with noncontact contributions (PSO and SD) as shown by recent calculations (108)(109)(110). Given also that unsaturated F-substituted carbon chains were used as quantum computers with five qubits (111), it is highly recommended to have a look on this kind of general systems.…”

Section: Nonrelativistic Ab Initio Schemesmentioning

confidence: 98%

Understanding NMR J‐couplings by the theory of polarization propagators

Aucar

2008

Concepts Magnetic Resonance

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Propagators are powerful theoretical tools that were first developed within the nonrelativistic (NR) regime and were applied to calculate atomic and molecular properties more than 30 years ago. The recent relativistic generalization of polarization propagators has shown that these propagators play a special role in describing the quantum origin of any molecular property and the broad implication of their particular definition. In this article, we give a general overview on fundamentals and applications of polarization propagators to one of the most important NMR spectroscopic parameters, the nuclear spin coupling mediated by the electronic system within both regimes: relativistic and NR. This presentation is given in a level that can be followed with a basic knowledge of quantum mechanics. Our aim is to show what one can learn about molecular electronic configurations, and also the transmission and influence of magnetic perturbations on electronic systems from basic theoretical elements like molecular orbitals, electronic excitation energies, coupling pathways, entanglement, etc. by using propagators. We shall use i) semiempirical models and ii) ab initio calculations at different levels of approach. We give a deep insight on the electronic origin of the Karplus' rule, the sign of indirect nuclear spin couplings, unusually large long-range couplings, cooperativity effects, relativistic effects, and the origin of diamagnetism. Some of these analysis are based on previous publications, and some others are presented here for the first ime.

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“…For all SSCC calculations, the specialised aug-cc-pVTZ-J basis set was used [26]. This basis set ensures the correct cusp behaviour of the wave function and consequently a very good description of the FC term [20]. The aug-cc-pVTZ-J basis set yields SSCCs close to those obtained with larger basis sets [20,[27][28][29].…”

Section: Computational Detailsmentioning

confidence: 99%

“…Calculated contributions and total SSCCs for the geminal 2 J FF in 1,2-difluoroethylene are represented in Figure 2. Also the contributions calculated by Contreras et al [20] at the SOPPA(CCSD) and the experimental value are displayed for comparison. DSO contributions were not plotted owing to its small variation with the HF exchange.…”

Section: Effect Of Exchange and Correlation Functionals Of Fluorine-fmentioning

confidence: 99%

Assessment of DFT functionals with fluorine–fluorine coupling constants

Vega

Fabián

2015

Molecular Physics

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Density functional theory (DFT) calculations of nuclear magnetic resonance (NMR) spin-spin coupling constants (SSCCs) provide an important contribution for understanding experimentally observed values. It is known that calculated SSCCs using DFT methods correlate well with those experimentally measured. Unlike most of SSCCs, in fluorine compounds, fluorine-fluorine SSCC J FF shows that the Fermi contact (FC) term is not dominant, particularly for J FF in polyfluorinated organic molecules. In order to devise a DFT approach that would correctly reproduce the variation of SSCCs within a series of fluorine compounds, we test several DFT-based approaches, using different exchange and correlation functionals. Isotropic contributions to NMR fluorine-fluorine coupling constants (FC, spin-dipolar, SD, paramagnetic spin-orbit, PSO, and diamagnetic spin-orbit, DSO) have been calculated. Results show that DFT methods give appropriate values for n J FF (n = 4 to 7), while for geminal and vicinal J FF present large deviations from experimental values. For the latter SSCCs ( 2 J FF and 3 J FF ), the four contributions (FC, SD, PSO and DSO) are analysed as a function of the local and nonlocal exchange in 1,1-and 1,2-difluoroethylene. Although FC term is not dominant for these SSCCs, the variation of this contribution with exchange is remarkable. On the other hand, SD and PSO contributions can be suitably computed without and with exact exchange, respectively.

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Substituent Effects on Scalar²J(¹⁹F,¹⁹F) and³J(¹⁹F,¹⁹F) NMR Couplings: A Comparison of SOPPA and DFT Methods

Cited by 104 publications

References 48 publications

Optimized basis sets for the calculation of indirect nuclear spin-spin coupling constants involving the atoms B, Al, Si, P, and Cl

Optimized basis sets for the calculation of indirect nuclear spin-spin coupling constants involving the atoms B, Al, Si, P, and Cl

Understanding NMR J‐couplings by the theory of polarization propagators

Assessment of DFT functionals with fluorine–fluorine coupling constants

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