Augmented Gaussian basis sets of double and triple zeta valence qualities for the atoms K and Sc–Kr: Applications in HF, MP2, and DFT calculations of molecular electric properties

Camiletti, Giuseppi Gava; Neto, A. Canal; Jorge, F.E.; Machado, S.F.

doi:10.1016/j.theochem.2009.06.024

Cited by 40 publications

(26 citation statements)

References 45 publications

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“…Geometry optimizations of all molecules considered in the present study were performed at nonrelativistic second‐order Møller–Plesset (MP2) level of theory using ATZP basis set with taking into account solvent effects within the integral equation formalism of polarizable continuum model, IEF‐PCM, in Gaussian 09 program package . The “ relativistic geometry factor ” has not been taken into account, since for the compounds considered in this study it results in a vanishingly small change.…”

Section: Computational Detailsmentioning

confidence: 99%

“…Basis set examination for the 1 H NMR shielding constants has been performed in Gaussian 09 program package at nonrelativistic Hartree–Fock (HF) and MP2 levels in combination with the “gauge‐including atomic orbitals” (GIAO) formalism . There were considered full Jorge's AXZP (X = D, T, Q) basis sets used on all atoms and the locally dense basis set (LDBS) schemes, implying AXZP (X = T, Q), on tellurium, selenium, and carbon atoms and Jensen's aug‐pcS‐2 basis set on the hydrogen atoms. In the Jensen's work, the aug‐pcS‐2 basis set has been shown to provide the most accurate results for proton shielding constants in a wide series of compounds in comparison with those provided by the most popular Pople's, Dunning's, and Ahlriches's triple‐ζ quality basis sets.…”

Section: Computational Detailsmentioning

confidence: 99%

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Long‐range relativistic heavy atom effect on ¹H NMR chemical shifts of selenium‐ and tellurium‐containing compounds

Rusakov

Rusakova

2018

Int J of Quantum Chemistry

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Previously unknown manifestation of heavy atom effect on the NMR chemical shifts of βand γ-protons initiated by the relativistic effects of the tellurium and selenium atoms has been investigated in the representative series of selenium-and tellurium-containing compounds. To approve the four-component density functional approach to be the appropriate tool for the investigation of the heavy atom on light atom effect (HALA), the benchmark calculations of the proton chemical shifts have been performed at the CCSD level using comprehensively chosen locally dense basis set with taking into account solvent, vibrational, and relativistic corrections.A good agreement with the experimental data was achieved. The magnitudes of the relativistic HALA corrections to βand γ-proton chemical shifts were found to vary in a wide range, namely from −3.08 ppm for the γ-proton of methyltelluraldehyde to 14.51 ppm for β-proton in benzotelluraldehyde. K E Y W O R D Schalcogens, 1 H NMR, HALA, relativistic effects | INTRODUCTIONAt the present day 1 H NMR spectroscopy plays a major role in the identification and structural elucidation of organic and organometallic compounds. Proton nucleus has very high intrinsic NMR sensitivity due to the significant natural abundance (>99.9%) of the 1 H hydrogen isotopes and a very high gyromagnetic ratio.Thus, proton NMR spectroscopy represents the most straightforward way of receiving structural information, even for the most problematic cases, when, for example, the concentration of a sample is very low.With the growth of computational capacities theoretical modeling of the proton NMR spectra (chemical shifts and spin-spin coupling constants) has become the one of the most powerful supplementary tools for solving structures in proton NMR spectroscopy. As a consequence, the accuracy of prediction of 1 H NMR chemical shifts and spin-spin coupling constants involving proton nuclei is of utmost importance at the present time.When treating the molecules, containing one or more heavy elements, not necessarily located in close vicinity to NMR protons under study, relativistic effects might come into play. The omission of the relativistic effects when modeling the 1 H NMR spectra of molecules containing heavy atoms usually results in the erroneous predictions, sometimes not even falling into the expected range. Thus, an influence of the relativistic effects on the 1 H NMR spectral parameters is one of the most important accuracy factors, which ought to be considered when dealing with the compounds containing heavy elements. An influence of the relativistic effects initiated by the presence of heavy atom (HA) on the nuclear shielding of light atom (LA) or spin-spin coupling constant between two LAs is called as relativistic HALA effect.It has been noticed that 1 H NMR chemical shifts are highly sensitive to the presence of heavy atoms. [1][2][3][4][5][6][7][8][9][10] At the first time HALA effect on proton NMR shielding constants was investigated as earlier as in the beginning of 1970s in hydrogen halides by ...

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Section: Computational Detailsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

Long‐range relativistic heavy atom effect on ¹H NMR chemical shifts of selenium‐ and tellurium‐containing compounds

Rusakov

Rusakova

2018

Int J of Quantum Chemistry

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“…Taking into account that no SARC‐ZORA basis sets are available for all the transition metals studied here, the all electron ADZP and the relativistic Stuttgart ECP basis set (denoted as SDD) were tested. Benchmark calculations on the fac ‐ and mer ‐[Rh(NO 3 ) 3 (H 2 O) 3 ] complexes, for which experimental data are available, revealed that the GIAO‐PBE0/ADZP(M)∪6‐31+G(d)(E)/PCM computational protocol performs better than the GIAO‐PBE0/SDD(M)∪6‐31+G(d)(E)/PCM one.…”

Section: Experimental Section and Computational Detailsmentioning

confidence: 99%

Aquanitrato Complexes of Palladium, Rhodium, and Platinum: A Comparative¹⁵N NMR and DFT Study

2018

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The accurate prediction of 15N nuclear magnetic resonance (NMR) chemical shifts for three sets of nitrato and mixed‐ligand aquanitrato rhodium (9 complexes), palladium (11 complexes) and platinum (11 complexes) systems was achieved using density functional theory (DFT) calculations employing the GIAO‐PBE0/ADZP(M)∪6‐31+G(d)(E)/PCM (M = Rh, Pd, or Pt, E = main group element) computational protocol. A comparison of δcalcd 15N NMR chemical shifts with δexptl 15N NMR chemical shifts reveals that the DFT calculations correctly predict the division of signals into two groups, the first one involving the PdII, PtII, and RhIII nitrato complexes, and the second the PtIV and PdIV nitrato complexes. Hydrogen bonds and the number of nitrato ligands and their coordination mode remarkably affect the δcalcd 15N chemical shift. Generally, the experimentally observed chemical shifts are found in a sufficiently narrower range for each metal center in comparison to the calculated ones due to an averaging action of the outer‐sphere interactions of complexes with external molecules of water and nitric acid.

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“…Three different exchange-correlation functionals: BLYP, B3LYP, BHLYP and two different basis sets have been used. In the first basis set, later referred to as basis set A, for all atoms the all-electron augmented triple-set with polarization functions (ATZP) [22][23][24] basis set has been used. For acetylene derivative containing lead ADZP basis set [25,26] was used instead of ATZP.…”

Section: Computational Detailsmentioning

confidence: 99%

Spin–spin coupling constants in $$\hbox {HC}{\equiv }\hbox {CXH}_3$$ HC ≡ CXH 3 molecules; $$\hbox {X}{=

2018

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The nuclear spin-spin coupling constants in a series of acetylene derivatives HC≡CXH 3 , where X is C, Si, Ge, Sn, Pb, have been calculated employing both coupled-cluster theory (CC) and density functional theory (DFT), the latter in nonrelativistic and relativistic four-component approach with different exchange-correlation functionals and basis sets. In addition, property derivatives with respect to molecular geometry parameters have been computed with nonrelativistic and relativistic Hamiltonians in order to evaluate the usefulness of the calculated nonrelativistic vibrational corrections. Generally, the CC method reproduces the experimental values somewhat better than DFT. In the case of the latter, the performance of B3LYP functional was the most satisfactory. The relativistic effects become noticeable for the couplings including heavy atom in tin-and lead-containing molecules. The calculations of the derivatives of the coupling constants indicate that these derivatives are even more sensitive to the relativistic effects than the corresponding coupling constants.

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Augmented Gaussian basis sets of double and triple zeta valence qualities for the atoms K and Sc–Kr: Applications in HF, MP2, and DFT calculations of molecular electric properties

Cited by 40 publications

References 45 publications

Long‐range relativistic heavy atom effect on ¹H NMR chemical shifts of selenium‐ and tellurium‐containing compounds

Long‐range relativistic heavy atom effect on ¹H NMR chemical shifts of selenium‐ and tellurium‐containing compounds

Aquanitrato Complexes of Palladium, Rhodium, and Platinum: A Comparative¹⁵N NMR and DFT Study

Spin–spin coupling constants in $$\hbox {HC}{\equiv }\hbox {CXH}_3$$ HC ≡ CXH 3 molecules; $$\hbox {X}{=

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Augmented Gaussian basis sets of double and triple zeta valence qualities for the atoms K and Sc–Kr: Applications in HF, MP2, and DFT calculations of molecular electric properties

Cited by 40 publications

References 45 publications

Long‐range relativistic heavy atom effect on 1H NMR chemical shifts of selenium‐ and tellurium‐containing compounds

Long‐range relativistic heavy atom effect on 1H NMR chemical shifts of selenium‐ and tellurium‐containing compounds

Aquanitrato Complexes of Palladium, Rhodium, and Platinum: A Comparative15N NMR and DFT Study

Spin–spin coupling constants in $$\hbox {HC}{\equiv }\hbox {CXH}_3$$ HC ≡ CXH 3 molecules; $$\hbox {X}{=

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Product

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Long‐range relativistic heavy atom effect on ¹H NMR chemical shifts of selenium‐ and tellurium‐containing compounds

Long‐range relativistic heavy atom effect on ¹H NMR chemical shifts of selenium‐ and tellurium‐containing compounds

Aquanitrato Complexes of Palladium, Rhodium, and Platinum: A Comparative¹⁵N NMR and DFT Study