Non-Covalent Interactions Atlas Benchmark Data Sets: Hydrogen Bonding

Dissociation Curves ◽

New Generation ◽

The Non-Covalent Interactions Atlas project (www.nciatlas.org) aims to cover a wide range of non-covalent interactions with a new generation of benchmark data sets. This paper presents the first two data sets focused on hydrogen bonding: HB375, featuring neutral systems, and IHB100 for ionic H-bonds. Both data sets are complemented by ten-point dissociation curves (HB375x10, IHB100x10). The interaction energies are extrapolated to the CCSD(T)/CBS limit from calculations in large basis sets. The paper also summarizes the design principles that will be used to construct the subsequent data sets in the series. The testing of DFT-D methods on the HB375 set has revealed interesting, previously unnoticed issues. The application of the new data to the testing and parameterization of semiempirical QM methods is also discussed.

Non-Covalent Interactions Atlas Benchmark Data Sets 2: Hydrogen Bonding in an Extended Chemical Space

10.26434/chemrxiv.12587537.v1 ◽

2020 ◽

Author(s):

Jan Řezáč

Keyword(s):

Hydrogen Bonding ◽

Organic Molecules ◽

Chemical Space ◽

Data Sets ◽

Data Set ◽

Benchmark Data ◽

Dissociation Curves ◽

New Generation ◽

The Non-Covalent Interactions Atlas (www.nciatlas.org) aims to provide a new generation of benchmark data sets for non-covalent interactions. The HB300SPX data set presented here extends the coverage of hydrogen bonds to phosphorus, sulfur and halogens up to iodine. It is again complemented by a set of dissociation curves, HB300SPX×10. The new data make it possible to analyze the transferability of the parametrization of e.g. dispersion corrections for DFT from simple organic molecules to a broader chemical space. The HB300SPX×10 has also been used for the extension of the parametrization of hydrogen-bonding corrections in the semiempirical PM6-D3H4X and DFTB3-D3H5 methods to additional elements.<br>

Non-Covalent Interactions Atlas Benchmark Data Sets 2: Hydrogen Bonding in an Extended Chemical Space

10.26434/chemrxiv.12587537 ◽

2020 ◽

Author(s):

Jan Řezáč

Keyword(s):

Hydrogen Bonding ◽

Organic Molecules ◽

Chemical Space ◽

Data Sets ◽

Data Set ◽

Benchmark Data ◽

Dissociation Curves ◽

New Generation ◽

The Non-Covalent Interactions Atlas (www.nciatlas.org) aims to provide a new generation of benchmark data sets for non-covalent interactions. The HB300SPX data set presented here extends the coverage of hydrogen bonds to phosphorus, sulfur and halogens up to iodine. It is again complemented by a set of dissociation curves, HB300SPX×10. The new data make it possible to analyze the transferability of the parametrization of e.g. dispersion corrections for DFT from simple organic molecules to a broader chemical space. The HB300SPX×10 has also been used for the extension of the parametrization of hydrogen-bonding corrections in the semiempirical PM6-D3H4X and DFTB3-D3H5 methods to additional elements.<br>

Non-Covalent Interactions Atlas Benchmark Data Sets 2: Hydrogen Bonding in an Extended Chemical Space

Journal of Chemical Theory and Computation ◽

10.1021/acs.jctc.0c00715 ◽

2020 ◽

Vol 16 (10) ◽

pp. 6305-6316

Author(s):

Jan Řezáč

Keyword(s):

Hydrogen Bonding ◽

Chemical Space ◽

Data Sets ◽

Benchmark Data ◽

Non-Covalent Interactions Atlas Benchmark Data Sets: Hydrogen Bonding

Journal of Chemical Theory and Computation ◽

10.1021/acs.jctc.9b01265 ◽

2020 ◽

Vol 16 (4) ◽

pp. 2355-2368 ◽

Cited By ~ 5

Author(s):

Jan Řezáč

Keyword(s):

Hydrogen Bonding ◽

Data Sets ◽

Benchmark Data ◽

Non-Covalent Interactions Atlas Benchmark Data Sets 3: Repulsive Contacts

Journal of Chemical Theory and Computation ◽

10.1021/acs.jctc.0c01341 ◽

2021 ◽

Vol 17 (3) ◽

pp. 1548-1561

Author(s):

Kristian Kříž ◽

Martin Nováček ◽

Jan Řezáč

Keyword(s):

Data Sets ◽

Benchmark Data ◽

Non-Covalent Interactions Atlas Benchmark Data Sets 3: Repulsive Contacts

10.26434/chemrxiv.13414931.v1 ◽

2020 ◽

Author(s):

Kristian Kříž ◽

Martin Nováček ◽

Jan Řezáč

Keyword(s):

Organic Molecules ◽

Energy Surface ◽

Molecular Complexes ◽

Data Sets ◽

Interaction Energies ◽

Data Set ◽

Benchmark Data ◽

Mechanical Methods ◽

The new R739×5 data set from the Non-Covalent Interactions Atlas series (www.nciatlas.org) focuses on repulsive contacts in molecular complexes, covering organic molecules, sulfur, phosphorus, halogens and noble gases. Information on the repulsive parts of the potential energy surface is crucial for the development of robust empirically parametrized computational methods. We use the new data set of highly accurate CCSD(T)/CBS interaction energies to test existing DFT and semiempirical quantum-mechanical methods. On the example of the PM6 method, we analyze the source of the error and its relation to the difficulties in the description of conformational energies, and we also devise an immediately applicable correction that fixes the most serious uncorrected issues previously encountered in practical calculations.

Non-Covalent Interactions Atlas Benchmark Data Sets 5: London Dispersion in an Extended Chemical Space

10.26434/chemrxiv-2022-pl3r8 ◽

2022 ◽

Author(s):

Jan Řezáč

Keyword(s):

Chemical Space ◽

Data Sets ◽

Dft Methods ◽

Data Set ◽

Data Points ◽

Comprehensive Test ◽

London Dispersion ◽

Dissociation Curves ◽

The Non-Covalent Interactions Atlas (www.nciatlas.org) has been extended with two data sets of benchmark interaction energies in complexes dominated by London dispersion. The D1200 data set of equilibrium geometries provides a thorough sampling of an extended chemical space, while the D442×10 set features dissociation curves for selected complexes. In total, they provide 5,178 new CCSD(T)/CBS data points of the highest quality. The new data have been combined with previous NCIA data sets in a comprehensive test of dispersion-corrected DFT methods, identifying the ones that achieve high accuracy in all types of non-covalent interactions in a broad chemical space. Additional tests of dispersion-corrected MP2 and semiempirical QM methods are also reported.

Non-Covalent Interactions Atlas Benchmark Data Sets 3: Repulsive Contacts

10.26434/chemrxiv.13414931 ◽

2020 ◽

Author(s):

Kristian Kříž ◽

Martin Nováček ◽

Jan Řezáč

Keyword(s):

Organic Molecules ◽

Energy Surface ◽

Molecular Complexes ◽

Data Sets ◽

Interaction Energies ◽

Data Set ◽

Benchmark Data ◽

Mechanical Methods ◽

The new R739×5 data set from the Non-Covalent Interactions Atlas series (www.nciatlas.org) focuses on repulsive contacts in molecular complexes, covering organic molecules, sulfur, phosphorus, halogens and noble gases. Information on the repulsive parts of the potential energy surface is crucial for the development of robust empirically parametrized computational methods. We use the new data set of highly accurate CCSD(T)/CBS interaction energies to test existing DFT and semiempirical quantum-mechanical methods. On the example of the PM6 method, we analyze the source of the error and its relation to the difficulties in the description of conformational energies, and we also devise an immediately applicable correction that fixes the most serious uncorrected issues previously encountered in practical calculations.

1,3,5-Triaza-7-Phosphaadamantane (PTA) as a 31P NMR Probe for Organometallic Transition Metal Complexes in Solution

Molecules ◽

10.3390/molecules26051390 ◽

2021 ◽

Vol 26 (5) ◽

pp. 1390 ◽

Cited By ~ 1

Author(s):

Ilya G. Shenderovich

Keyword(s):

Chemical Shift ◽

Transition Metal ◽

Metal Complexes ◽

Transition Metal Complexes ◽

Density Functional ◽

Molecular Structures ◽

Basis Sets ◽

Functional Theory ◽

Due to the rigid structure of 1,3,5-triaza-7-phosphaadamantane (PTA), its 31P chemical shift solely depends on non-covalent interactions in which the molecule is involved. The maximum range of change caused by the most common of these, hydrogen bonding, is only 6 ppm, because the active site is one of the PTA nitrogen atoms. In contrast, when the PTA phosphorus atom is coordinated to a metal, the range of change exceeds 100 ppm. This feature can be used to support or reject specific structural models of organometallic transition metal complexes in solution by comparing the experimental and Density Functional Theory (DFT) calculated values of this 31P chemical shift. This approach has been tested on a variety of the metals of groups 8–12 and molecular structures. General recommendations for appropriate basis sets are reported.