New efficient pecS-n (n = 1, 2) basis sets for quantum chemical calculations of 31P NMR chemical shifts

Rusakov, Yury Yu.; Rusakova, Irina L.

doi:10.1039/d3cp02664g

Cited by 3 publications

(5 citation statements)

References 114 publications

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“…0.46/0.25 ppm for 1 H, 4.47/2.09 ppm for 13 C, 7.0/3.28 ppm for 15 N, 9.85/6.92 ppm for 31 P, 4.31/2.08 ppm for 19 F, and 4.67/3.13 ppm for 29 Si, calculated on the CCSD or (/) DFT(B97-2) equilibrium geometries, respectively. These are very considerable numbers, given that the best contemporary accuracy of the NMR chemical shift calculations can be characterized by absolute deviations from the experiment of about 0.3–0.5 ppm for 1 H, − 1–2 ppm for 13 C, − 5–6 ppm for 15 N, , 4–5 ppm for 31 P, ,, 1–5 ppm for 19 F, , and 5–7 ppm for 29 Si. , …”

Section: Results and Discussionmentioning

confidence: 99%

“…The red numbers designate the sizes of the basis sets for 3p elements. ppm for 15 N, 95,97 4−5 ppm for 31 P, 48,98,99 1−5 ppm for F, 100,101 and 5−7 ppm for 29 Si. 102,103 At the same time, using the most popular 6-311G(d,p) basis set of triple-ζ quality in the geometry optimization performed with the CCSD and DFT(B97-2) methods decreases the mean geometry factor error for NMR shielding constants of each type of nuclei by about 2 and 3 times, respectively, as compared to the geometry factor error coming from the geometries optimized with the cc-pVDZ basis set.…”

Section: Assessing the Performance Of The Pecg-n (N = 1 2) Basis Sets...mentioning

confidence: 99%

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Getaway from the Geometry Factor Error in the Molecular Property Calculations: Efficient pecG-n (n = 1, 2) Basis Sets for the Geometry Optimization of Molecules Containing Light p Elements

Rusakov,

Rusakova

2024

J. Chem. Theory Comput.

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The basis of all molecular property quantum chemical calculations is the correct equilibrium geometry. In this paper, new efficient pecG-n (n = 1, 2) basis sets for the geometry optimization of molecules containing hydrogen and p elements of 2−3 periods are proposed. These basis sets were optimized via the property-energy consistent (PEC) algorithm directed to the minimization of the molecular energy gradient relative to the bond lengths. New basis sets are compact and give equilibrium geometries of very high quality, which is comparable to that provided by considerably larger energy-optimized basis sets. The equilibrium geometries obtained with the pecG-n (n = 1, 2) basis sets and the other basis sets of diverse quality were tested in the CCSD calculations of different second-order molecular properties, including NMR shielding constants, static polarizabilities, and static magnetizabilities. As a result, new basis sets have demonstrated far superior performance as compared to the other energy-optimized basis sets of the same or close sizes commonly used at the geometry optimization stage.

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Section: Results and Discussionmentioning

confidence: 99%

Section: Assessing the Performance Of The Pecg-n (N = 1 2) Basis Sets...mentioning

confidence: 99%

Getaway from the Geometry Factor Error in the Molecular Property Calculations: Efficient pecG-n (n = 1, 2) Basis Sets for the Geometry Optimization of Molecules Containing Light p Elements

Rusakov,

Rusakova

2024

J. Chem. Theory Comput.

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“…Practically all of them represent very important species with po-tential biological activity. The considered compounds include 10 -hydroxyusambarensine (1), 2-2-di(3-indolyl)-3-indolone (2), acantholactam (3), alasmontamine A (4), anabsinthin (5), asperlicin (6), chetomin (7), diosgenin-3-O-β-D-glucopyranoside (8), itoaic acid (9), jaspamide Q (10), korundamine A (11), limonin (12), matopensine (13), mulberrofuran G ( 14), 1α,8β,9β,14α,15β-pentaacetoxy-3β-benzoyloxy-7-oxojatropha-5,12-diene (15), pedunculagin (16), phyllaemblicin B (17), physalin D (18), procyanidin B2 (19), strychnine (20), strychnobaillonine (21), terrequinone A (22), and viomycin (23).…”

Section: Benchmark Calculationsmentioning

confidence: 99%

“…The development of the δ-oriented basis sets continues today. We also have introduced recently new effective δ-oriented basis sets, viz., the pecS-n (n = 1, 2), purposed for the calculations of 1 H, 13 C, 15 N, 17 O, and 31 P NMR chemical shifts [22,23], which were optimized using the property-energy consistent (PEC) method [24]. The pecS-1/pecS-2 basis sets consisting of only 5/14 and 18/34 functions for hydrogen and carbon atoms, respectively, demonstrated a very good accuracy against the experiment.…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, we also watched the pecS-n basis sets manifesting a remarkable robustness of the results in relation to the choice of the XC functional used. In all respects, our NMR-oriented basis sets [22][23][24][25][26] showed a fine balance between size and accuracy, which makes them a promising tool in demanding DFT calculations of the NMR parameters of large natural products.…”

Section: Introductionmentioning

confidence: 99%

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On the Efficiency of the Density Functional Theory (DFT)-Based Computational Protocol for 1H and 13C Nuclear Magnetic Resonance (NMR) Chemical Shifts of Natural Products: Studying the Accuracy of the pecS-n (n = 1, 2) Basis Sets

Rusakov,

Semenov,

Rusakova

2023

IJMS

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The basis set issue has always been one of the most important factors of accuracy in the quantum chemical calculations of NMR chemical shifts. In a previous paper, we developed new pecS-n (n = 1, 2) basis sets purposed for the calculations of the NMR chemical shifts of the nuclei of the most popular NMR-active isotopes of 1–2 row elements and successfully approbated these on the DFT calculations of chemical shifts in a limited series of small molecules. In this paper, we demonstrate the performance of the pecS-n (n = 1, 2) basis sets on the calculations of as much as 713 1H and 767 13C chemical shifts of 23 biologically active natural products with complicated stereochemical structures, carried out using the GIAO-DFT(PBE0) approach. We also proposed new alternative contraction schemes for our basis sets characterized by less contraction depth of the p-shell. New contraction coefficients have been optimized with the property-energy consistent (PEC) method. The accuracies of the pecS-n (n = 1, 2) basis sets of both the original and newly contracted forms were assessed on massive benchmark calculations of proton and carbon chemical shifts of a vast variety of natural products. It was found that less contracted pecS-n (n = 1, 2) basis sets provide no noticeable improvement in accuracy. These calculations represent the most austere test of our basis sets as applied to routine calculations of the NMR chemical shifts of real-life compounds.

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On the utmost importance of the geometry factor of accuracy in the quantum chemical calculations of 31P NMR chemical shifts: New efficient pecG-n (n = 1, 2) basis sets for the geometry optimization procedure

Rusakov,

Nikurashina,

Rusakova

2024

The Journal of Chemical Physics

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31P nuclear magnetic resonance (NMR) chemical shifts were shown to be very sensitive to the basis set used at the geometry optimization stage. Commonly used energy-optimized basis sets for a phosphorus atom containing only one polarization d-function were shown to be unable to provide correct equilibrium geometries for the calculations of phosphorus chemical shifts. The use of basis sets with at least two polarization d-functions on a phosphorus atom is strongly recommended. In this paper, an idea of creating the basis sets purposed for the geometry optimization that provide the least possible error coming from the geometry factor of accuracy in the resultant NMR shielding constants is proposed. The property-energy consisted algorithm with the target function in the form of the molecular energy gradient relative to P–P bond lengths was applied to create new geometry-oriented pecG-n (n = 1, 2) basis sets for a phosphorus atom. New basis sets have demonstrated by far superior performance as compared to the other commonly used energy-optimized basis sets in massive calculations of 31P NMR chemical shifts carried out at the gauge-including atomic orbital-coupled cluster singles and doubles/pecS-2 level of the theory by taking into account solvent, vibrational, and relativistic corrections.

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New efficient pecS-n (n = 1, 2) basis sets for quantum chemical calculations of ³¹P NMR chemical shifts

Abstract: The basis sets that are used in the quantum chemical calculations of 31P NMR chemical shifts have ever been one of the most important factors of accuracy. Regardless of what...

Cited by 3 publications

References 114 publications

Getaway from the Geometry Factor Error in the Molecular Property Calculations: Efficient pecG-n (n = 1, 2) Basis Sets for the Geometry Optimization of Molecules Containing Light p Elements

Getaway from the Geometry Factor Error in the Molecular Property Calculations: Efficient pecG-n (n = 1, 2) Basis Sets for the Geometry Optimization of Molecules Containing Light p Elements

On the Efficiency of the Density Functional Theory (DFT)-Based Computational Protocol for 1H and 13C Nuclear Magnetic Resonance (NMR) Chemical Shifts of Natural Products: Studying the Accuracy of the pecS-n (n = 1, 2) Basis Sets

On the utmost importance of the geometry factor of accuracy in the quantum chemical calculations of 31P NMR chemical shifts: New efficient pecG-n (n = 1, 2) basis sets for the geometry optimization procedure

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