Augmented Gaussian basis sets for the elements K, Sc–Kr, Rb, and Y–Xe: Application in HF, MP2, and DFT calculations of molecular electric properties

Martins, L.S.C.; Souza, Fábio A. L. de; Ceolin, G.A.; Jorge, F.E.; Berrêdo, R.C. de; Campos, C.T.

doi:10.1016/j.comptc.2013.03.004

Cited by 54 publications

(36 citation statements)

References 52 publications

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“…All calculations used a 6-311+G(2d,p) basis 64–67 for all atoms on the central monomer of interest, a 6-311G(d,p) basis for all neighboring atoms out to 4 Å, and a 6-31G 68,69 basis for all atoms beyond 4 Å. This locally dense basis set 70,71 combination has proved effective in previous studies 12,72 and is simply referred to here as our “mixed basis.” The ATZP basis 73 was used on the tin atom for the nitrosoarene in Section 7.4.…”

Section: Methodsmentioning

confidence: 99%

Benchmark fragment-based¹H,¹³C,¹⁵N and¹⁷O chemical shift predictions in molecular crystals

Hartman

Kudla

Day

et al. 2016

Phys. Chem. Chem. Phys.

107

260

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The performance of fragment-based ab initio 1H, 13C, 15N and 17O chemical shift predictions is assessed against experimental NMR chemical shift data in four benchmark sets of molecular crystals. Employing a variety of commonly used density functionals (PBE0, B3LYP, TPSSh, OPBE, PBE, TPSS), we explore the relative performance of cluster, two-body fragment, and combined cluster/fragment models. The hybrid density functionals (PBE0, B3LYP and TPSSh) generally out-perform their generalized gradient approximation (GGA)-based counterparts. 1H, 13C, 15N, and 17O isotropic chemical shifts can be predicted with root-mean-square errors of 0.3, 1.5, 4.2, and 9.8 ppm, respectively, using a computationally inexpensive electrostatically embedded two-body PBE0 fragment model. Oxygen chemical shieldings prove particularly sensitive to local many-body effects, and using a combined cluster/fragment model instead of the simple two-body fragment model decreases the root-mean-square errors to 7.6 ppm. These fragment-based model errors compare favorably with GIPAW PBE ones of 0.4, 2.2, 5.4, and 7.2 ppm for the same 1H, 13C, 15N, and 17O test sets. Using these benchmark calculations, a set of recommended linear regression parameters for mapping between calculated chemical shieldings and observed chemical shifts are provided and their robustness assessed using statistical cross-validation. We demonstrate the utility of these approaches and the reported scaling parameters on applications to 9-tertbutyl anthracene, several histidine co-crystals, benzoic acid and the C-nitrosoarene SnCl2(CH3)2(NODMA)2.

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Section: Methodsmentioning

confidence: 99%

Benchmark fragment-based¹H,¹³C,¹⁵N and¹⁷O chemical shift predictions in molecular crystals

Hartman

Kudla

Day

et al. 2016

Phys. Chem. Chem. Phys.

107

260

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“…35 For I, the TZ and QZ valence basis sets by Peterson et al were used in combination with ECP28MDF, 40 whereas the TZ and QZ valence basis set by Martin and Sunderman were used with ECP46MWB. 36 For At, the DZ valence basis set by Kuechle et al was used with ECP78MHF, 41 whereas the DZ valence basis set for ECP78MDF was optimised by Stoll et al 38 An all-electron calculation was also performed for C 6 I 2+ 6 using the iodine ATZP basis set by Martins et al 42 In the ECP calculations, the def2-TZVP basis set was used for carbon. 25 Current densities (susceptibilities) and ring-current (susceptibility) strengths were calculated with GIMIC.…”

Section: Methodsmentioning

confidence: 99%

Calculations of current densities for neutral and doubly charged persubstituted benzenes using effective core potentials

Rauhalahti

Taubert

Sundholm

et al. 2017

Phys. Chem. Chem. Phys.

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Magnetically induced current density susceptibilities and ring-current strengths have been calculated for neutral and doubly charged persubstituted benzenes CX and CX with X = F, Cl, Br, I, At, SeH, SeMe, TeH, TeMe, and SbH. The current densities have been calculated using the gauge-including magnetically induced current (GIMIC) method, which has been interfaced to the Gaussian electronic structure code rendering current density calculations using effective core potentials (ECP) feasible. Relativistic effects on the ring-current strengths have been assessed by employing ECP calculations of the current densities. Comparison of the ring-current strengths obtained in calculations on CAt and CAt using relativistic and non-relativistic ECPs show that scalar relativistic effects have only a small influence on the ring-current strengths. Comparisons of the ring-current strengths and ring-current profiles show that the CI, CAt, C(SeH), C(SeMe), C(TeH), C(TeMe), and C(SbH) dications are doubly aromatic sustaining spatially separated ring currents in the carbon ring and in the exterior of the molecule. The CI radical cation is also found to be doubly aromatic with a weaker ring current than obtained for the dication.

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“…40 There are not too many all-electron basis sets available for all the atoms studied in this work. We shall report the results obtained with the uncontracted ANO-RCC basis sets; 41 we have also performed test calculations applying the uncontracted AQZP basis 42,43 and the dyall-cvtz basis set (see below). The results were very similar; therefore at the CCSD level we have not analyzed further the basis set dependence.…”

Section: Methodsmentioning

confidence: 99%

Indirect NMR spin–spin coupling constants in diatomic alkali halides

Jaszuński

Antušek

Demissie

et al. 2016

The Journal of Chemical Physics

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We report the Nuclear Magnetic Resonance (NMR) spin-spin coupling constants for diatomic alkali halides MX, where M = Li, Na, K, Rb, or Cs and X = F, Cl, Br, or I. The coupling constants are determined by supplementing the non-relativistic coupled-cluster singles-and-doubles (CCSD) values with relativistic corrections evaluated at the four-component density-functional theory (DFT) level. These corrections are calculated as the differences between relativistic and non-relativistic values determined using the PBE0 functional with 50% exact-exchange admixture. The total coupling constants obtained in this approach are in much better agreement with experiment than the standard relativistic DFT values with 25% exact-exchange, and are also noticeably better than the relativistic PBE0 results obtained with 50% exact-exchange. Further improvement is achieved by adding rovibrational corrections, estimated using literature data. Published by AIP Publishing. [http://dx

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Augmented Gaussian basis sets for the elements K, Sc–Kr, Rb, and Y–Xe: Application in HF, MP2, and DFT calculations of molecular electric properties

Cited by 54 publications

References 52 publications

Benchmark fragment-based¹H,¹³C,¹⁵N and¹⁷O chemical shift predictions in molecular crystals

Benchmark fragment-based¹H,¹³C,¹⁵N and¹⁷O chemical shift predictions in molecular crystals

Calculations of current densities for neutral and doubly charged persubstituted benzenes using effective core potentials

Indirect NMR spin–spin coupling constants in diatomic alkali halides

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Augmented Gaussian basis sets for the elements K, Sc–Kr, Rb, and Y–Xe: Application in HF, MP2, and DFT calculations of molecular electric properties

Cited by 54 publications

References 52 publications

Benchmark fragment-based1H,13C,15N and17O chemical shift predictions in molecular crystals

Benchmark fragment-based1H,13C,15N and17O chemical shift predictions in molecular crystals

Calculations of current densities for neutral and doubly charged persubstituted benzenes using effective core potentials

Indirect NMR spin–spin coupling constants in diatomic alkali halides

Contact Info

Product

Resources

About

Benchmark fragment-based¹H,¹³C,¹⁵N and¹⁷O chemical shift predictions in molecular crystals

Benchmark fragment-based¹H,¹³C,¹⁵N and¹⁷O chemical shift predictions in molecular crystals