Prediction of water's isotropic nuclear shieldings and indirect nuclear spin–spin coupling constants (SSCCs) using correlation‐consistent and polarization‐consistent basis sets in the Kohn–Sham basis set limit

Kupka, Teobald

doi:10.1002/mrc.2369

Cited by 36 publications

(25 citation statements)

References 84 publications

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“…BHandH density functional was success-ful in predicting water coupling constants, 112 for example, it fairly well reproduced the experimental value of 1 J OH and also showed the dominating role of Fermi contact term (FC).…”

Section: Dft Predicted Indirect Spin-spin Coupling Constants In DImentioning

confidence: 57%

Theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis-, and trans-1,2-difluoroethylenes

Nozirov

Kupka²,

Stachów

2014

The Journal of Chemical Physics

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A theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis- and trans-1,2-difluoroethylenes is reported. The results obtained using density functional theory (DFT) combined with large basis sets and gauge-independent atomic orbital calculations were critically compared with experiment and conventional, higher level correlated electronic structure methods. Accurate structural, vibrational, and NMR parameters of difluoroethylenes were obtained using several density functionals combined with dedicated basis sets. B3LYP/6-311++G(3df,2pd) optimized structures of difluoroethylenes closely reproduced experimental geometries and earlier reported benchmark coupled cluster results, while BLYP/6-311++G(3df,2pd) produced accurate harmonic vibrational frequencies. The most accurate vibrations were obtained using B3LYP/6-311++G(3df,2pd) with correction for anharmonicity. Becke half and half (BHandH) density functional predicted more accurate (19)F isotropic shieldings and van Voorhis and Scuseria's τ-dependent gradient-corrected correlation functional yielded better carbon shieldings than B3LYP. A surprisingly good performance of Hartree-Fock (HF) method in predicting nuclear shieldings in these molecules was observed. Inclusion of zero-point vibrational correction markedly improved agreement with experiment for nuclear shieldings calculated by HF, MP2, CCSD, and CCSD(T) methods but worsened the DFT results. The threefold improvement in accuracy when predicting (2)J(FF) in 1,1-difluoroethylene for BHandH density functional compared to B3LYP was observed (the deviations from experiment were -46 vs. -115 Hz).

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Section: Dft Predicted Indirect Spin-spin Coupling Constants In DImentioning

confidence: 57%

Theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis-, and trans-1,2-difluoroethylenes

Nozirov

Kupka²,

Stachów

2014

The Journal of Chemical Physics

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“…One might expect that, in the case of numerical calculations of anharmonic frequencies, the quality of the results could be influenced by the accuracy of the density grid, as in the case of the indirect spin–spin coupling constant [36, 39]. Detailed analysis of water and formaldehyde B3LYP frequency deviation from experimental values [40, 41], calculated with Pople and polarization-consistent basis sets, is shown in Tables 1 and 2, respectively.…”

Section: Resultsmentioning

confidence: 99%

Extrapolation of water and formaldehyde harmonic and anharmonic frequencies to the B3LYP/CBS limit using polarization consistent basis sets

2010

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The harmonic and anharmonic frequencies of fundamental vibrations in formaldehyde and water were successfully estimated using the B3LYP Kohn-Sham limit. The results obtained with polarization- and correlation-consistent basis sets were fitted with a two-parameter formula. Anharmonic corrections were obtained by a second order perturbation treatment (PT2). We compared the performance of the PT2 scheme on the two title molecules using SCF, MP2 and DFT (BLYP, B3LYP, PBE and B3PW91 functionals) methods combined with polarization consistent pc-n (n = 0, 1, 2, 3, 4) basis sets, Dunning’s basis sets (aug)-cc-pVXZ where X = D, T, Q, 5, 6 and Pople’s basis sets up to 6-311++G(3df,2pd). The influence of SCF convergence level and density grid size on the root mean square of harmonic and anharmonic frequency deviations from experimental values was tested. The wavenumber of formaldehyde CH2 anharmonic asymmetric stretching mode is very sensitive to grid size for large basis sets; this effect is not observed for harmonic modes. BLYP-calculated anharmonic frequencies consistently underestimate observed wavenumbers. On the basis of formaldehyde anharmonic frequencies, we show that increasing the Pople basis set size does not always lead to improved agreement between anharmonic frequencies and experimental values.FigureSensitivity of water B3LYP calculated harmonic and anharmonic vs(OH) frequencies on selected Pople and polarization consistent basis sets size. The results for pc-n basis sets were fitted with two parameter formula and the CBS(2,3,4) estimatedElectronic supplementary materialThe online version of this article (doi:10.1007/s00894-010-0913-3) contains supplementary material, which is available to authorized users.

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“…The other option for reliable prediction of SSCC parameters (not considered in the current study) could be specially modified ccJ‐pVXZ Dunning‐type basis sets with tight functions. In addition, a very fine density grid is required in case of DFT calculated SSCC parameters …”

Section: Resultsmentioning

confidence: 99%

Convergence of nuclear magnetic shieldings and one‐bond ¹J(¹¹B¹H) indirect spin–spin coupling constants in small boron molecules

Kupka

Buczek

Broda

et al. 2018

Magnetic Reson in Chemistry

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

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Prediction of water's isotropic nuclear shieldings and indirect nuclear spin–spin coupling constants (SSCCs) using correlation‐consistent and polarization‐consistent basis sets in the Kohn–Sham basis set limit

Cited by 36 publications

References 84 publications

Theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis-, and trans-1,2-difluoroethylenes

Theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis-, and trans-1,2-difluoroethylenes

Extrapolation of water and formaldehyde harmonic and anharmonic frequencies to the B3LYP/CBS limit using polarization consistent basis sets

Convergence of nuclear magnetic shieldings and one‐bond ¹J(¹¹B¹H) indirect spin–spin coupling constants in small boron molecules

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Prediction of water's isotropic nuclear shieldings and indirect nuclear spin–spin coupling constants (SSCCs) using correlation‐consistent and polarization‐consistent basis sets in the Kohn–Sham basis set limit

Cited by 36 publications

References 84 publications

Theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis-, and trans-1,2-difluoroethylenes

Theoretical prediction of nuclear magnetic shieldings and indirect spin-spin coupling constants in 1,1-, cis-, and trans-1,2-difluoroethylenes

Extrapolation of water and formaldehyde harmonic and anharmonic frequencies to the B3LYP/CBS limit using polarization consistent basis sets

Convergence of nuclear magnetic shieldings and one‐bond 1J(11B1H) indirect spin–spin coupling constants in small boron molecules

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Convergence of nuclear magnetic shieldings and one‐bond ¹J(¹¹B¹H) indirect spin–spin coupling constants in small boron molecules