The aug‐cc‐pVTZ‐J basis set for the <i>p</i>‐block fourth‐row elements Ga, Ge, As, Se, and Br

Steinmann, Casper; Sauer, Stephan P. A.

doi:10.1002/mrc.5166

Cited by 7 publications

(7 citation statements)

References 86 publications

(83 reference statements)

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“…This approach can be thought of as the most straightforward one because it is based on the consecutive augmentation of the important angular spaces using a recurrent ratio (geometrical progression, at most). In this respect, it should be mentioned that such an approach was used to obtain the now-popular aug-cc-pVTZ-J series of basis sets for different elements [80,[84][85][86][87][88][89][90][91]; the Pople-style basis sets 6-31G-J and 6-311G-J [92]; the acvXz-J for Se, Te, and Sn [93,94]; and the av3z-J for Te [41]. The other approaches involve, in some way or another, the optimization procedure, namely the search for the values of additional exponents is carried out via the variational procedure.…”

Section: Introductionmentioning

confidence: 99%

“…Only a few J-oriented basis sets for selenium exist at the moment, and all of them are rather large to be efficiently used in large-scale calculations. These are the acvXz-J (X = 2, 3, 4) [93], the aug-cc-pVTZ-J (the first version) [86], and the aug-cc-pVTZ-J (the second version) [87]. The aug-cc-pVTZ-J (the first version) basis set for selenium was obtained from the energy-optimized uncontracted Dunning's basis set of triple-zeta quality, aug-cc-pVTZ(uc) (21s14p10d2f ) [105], by the addition of two tight s-type functions and the subsequent application of the contraction scheme based on the molecular orbital coefficients of the selenium hydride, (23s14p10d2f ) -> [12s9p6d2f ].…”

Section: Introductionmentioning

confidence: 99%

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New pecJ-n (n = 1, 2) Basis Sets for Selenium Atom Purposed for the Calculations of NMR Spin–Spin Coupling Constants Involving Selenium

Rusakov

Rusakova

2023

IJMS

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We present new compact pecJ-n (n = 1, 2) basis sets for the selenium atom developed for the quantum–chemical calculations of NMR spin–spin coupling constants (SSCCs) involving selenium nuclei. These basis sets were obtained at the second order polarization propagator approximation with coupled cluster singles and doubles amplitudes (SOPPA(CCSD)) level with the property-energy consistent (PEC) method, which was introduced in our previous papers. The existing SSCC-oriented selenium basis sets are rather large in size, while the PEC method gives more compact basis sets that are capable of providing accuracy comparable to that reached using the property-oriented basis sets of larger sizes generated with a standard even-tempered technique. This is due to the fact that the PEC method is very different in its essence from the even-tempered approaches. It generates new exponents through the total optimization of angular spaces of trial basis sets with respect to the property under consideration and the total molecular energy. New basis sets were tested on the coupled cluster singles and doubles (CCSD) calculations of SSCCs involving selenium in the representative series of molecules, taking into account relativistic, solvent, and vibrational corrections. The comparison with the experiment showed that the accuracy of the results obtained with the pecJ-2 basis set is almost the same as that provided by a significantly larger basis set, aug-cc-pVTZ-J, while that achieved with a very compact pecJ-1 basis set is only slightly inferior to the accuracy provided by the former.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

New pecJ-n (n = 1, 2) Basis Sets for Selenium Atom Purposed for the Calculations of NMR Spin–Spin Coupling Constants Involving Selenium

Rusakov

Rusakova

2023

IJMS

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“…In the nonrelativistic level of theory, many efforts have been made to develop efficient specialized basis sets for NMR properties in order to decrease the computational costs of their quantum-chemical calculations. In particular, there were many specialized basis sets introduced for spin-spin coupling constants ( J -oriented basis sets) [ 52 , 59 , 60 , 61 , 62 , 63 , 64 , 65 , 66 , 67 , 68 , 69 , 70 , 71 , 72 , 73 ] and, to a lesser extent, for chemical shifts or shielding constants (σ-oriented basis sets) [ 51 , 74 , 75 , 76 ]. At the same time, for the relativistic level of theory, the issue of specialized basis sets for NMR parameters still remains open.…”

Section: Introductionmentioning

confidence: 99%

On the Utmost Importance of the Basis Set Choice for the Calculations of the Relativistic Corrections to NMR Shielding Constants

Rusakova

Rusakov

2023

IJMS

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The investigation of the sensitivity of the relativistic corrections to the NMR shielding constants (σ) to the configuration of angular spaces of the basis sets used on the atoms of interest was carried out within the four-component density functional theory (DFT). Both types of relativistic effects were considered, namely the so-called heavy atom on light atom and heavy atom on heavy atom effects, though the main attention was paid to the former. As a main result, it was found that the dependence of the relativistic corrections to σ of light nuclei (exemplified here by 1H and 13C) located in close vicinity to a heavy atom (exemplified here by In, Sn, Sb, Te, and I) on the basis set used on the light spectator atom was very much in common with that of the Fermi-contact contribution to the corresponding nonrelativistic spin-spin coupling constant (J). In general, it has been shown that the nonrelativistic J-oriented and σ-oriented basis sets, artificially saturated in the tight s-region, provided much better accuracy than the standard nonrelativistic σ-oriented basis sets when calculating the relativistic corrections to the NMR shielding constants of light nuclei at the relativistic four-component level of the DFT theory.

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“…From this, DFT appears to be the obvious choice for this articles’ computational explorations. Additionally, since the initial investigation by Grampp et al [ 10 ], ESR/NMR optimised J-augmented basis sets have become widely available [ 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 ], hence improvement of correlation with experimental and calculated couplings is promising.…”

Section: Introductionmentioning

confidence: 99%

A Combined Experimental and Theoretical Study of ESR Hyperfine Coupling Constants for N,N,N’,N’-Tetrasubstituted p-Phenylenediamine Radical Cations

Gleeson

Andersen

Rapta

et al. 2023

IJMS

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A test set of N,N,N’,N’-tetrasubstituted p-phenylenediamines are experimentally explored using ESR (electron spin resonance) spectroscopy and analysed from a computational standpoint thereafter. This computational study aims to further aid structural characterisation by comparing experimental ESR hyperfine coupling constants (hfccs) with computed values calculated using ESR-optimised “J-style” basis sets (6-31G(d,p)-J, 6-31G(d,p)-J, 6-311++G(d,p)-J, pcJ-1, pcJ-2 and cc-pVTZ-J) and hybrid-DFT functionals (B3LYP, PBE0, TPSSh, ωB97XD) as well as MP2. PBE0/6-31g(d,p)-J with a polarised continuum solvation model (PCM) correlated best with the experiment, giving an R2 value of 0.8926. A total of 98% of couplings were deemed satisfactory, with five couplings observed as outlier results, thus degrading correlation values significantly. A higher-level electronic structure method, namely MP2, was sought to improve outlier couplings, but only a minority of couples showed improvement, whilst the remaining majority of couplings were negatively degraded.

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The aug‐cc‐pVTZ‐J basis set for the p‐block fourth‐row elements Ga, Ge, As, Se, and Br

Abstract: The aug-cc-pVTZ-J basis set family is extended to include the fourth-row p-block elements Ga, Ge, As, Se, and Br. We use the established approach outlined by Sauer and coworkers (

Cited by 7 publications

References 86 publications

New pecJ-n (n = 1, 2) Basis Sets for Selenium Atom Purposed for the Calculations of NMR Spin–Spin Coupling Constants Involving Selenium

New pecJ-n (n = 1, 2) Basis Sets for Selenium Atom Purposed for the Calculations of NMR Spin–Spin Coupling Constants Involving Selenium

On the Utmost Importance of the Basis Set Choice for the Calculations of the Relativistic Corrections to NMR Shielding Constants

A Combined Experimental and Theoretical Study of ESR Hyperfine Coupling Constants for N,N,N’,N’-Tetrasubstituted p-Phenylenediamine Radical Cations

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