Evaluating Transition Metal Barrier Heights with the Latest DFT Exchange–Correlation Functionals – the MOBH35 Benchmark Dataset

A new database of transition metal reaction barrier heights – MOBH35 – is presented. Benchmark energies (forward and reverse barriers and reaction energy) are calculated using DLPNO-CCSD(T) extrapolated to the complete basis set limit using a Weizmann1-like scheme. Using these benchmark energies, the performance of a wide selection of density functional theory (DFT) exchange–correlation functionals, including the latest from the Truhlar and Head-Gordon groups, is evaluated. It was found, using the def2-TZVPP basis set, that the ωB97M-V (MAD 1.8 kcal/mol), ωB97X-V (MAD 2.1 kcal/mol) and SCAN0 (MAD 2.1 kcal/mol) hybrid functionals are recommended. The double-hybrid functionals PWPB95 (MAD 1.6 kcal/mol) and B2K-PLYP (MAD 1.8 kcal/mol) did perform slightly better but this has to be balanced by their increased computational cost.

Evaluating Transition Metal Barrier Heights with the Latest DFT Exchange–Correlation Functionals – the MOBH35 Benchmark Dataset

10.26434/chemrxiv.7732262 ◽

2019 ◽

Author(s):

Mark Iron ◽

Trevor Janes

Keyword(s):

Transition Metal ◽

Density Functional ◽

Computational Cost ◽

Basis Set ◽

Functional Theory ◽

Exchange Correlation ◽

Barrier Heights ◽

Complete Basis Set ◽

A new database of transition metal reaction barrier heights – MOBH35 – is presented. Benchmark energies (forward and reverse barriers and reaction energy) are calculated using DLPNO-CCSD(T) extrapolated to the complete basis set limit using a Weizmann1-like scheme. Using these benchmark energies, the performance of a wide selection of density functional theory (DFT) exchange–correlation functionals, including the latest from the Truhlar and Head-Gordon groups, is evaluated. It was found, using the def2-TZVPP basis set, that the ωB97M-V (MAD 1.8 kcal/mol), ωB97X-V (MAD 2.1 kcal/mol) and SCAN0 (MAD 2.1 kcal/mol) hybrid functionals are recommended. The double-hybrid functionals PWPB95 (MAD 1.6 kcal/mol) and B2K-PLYP (MAD 1.8 kcal/mol) did perform slightly better but this has to be balanced by their increased computational cost.

How Accurate Are Static Polarizability Predictions from Density Functional Theory? An Assessment over 132 Species at Equilibrium Geometry

10.26434/chemrxiv.6449693 ◽

2018 ◽

Author(s):

Diptarka Hait ◽

Martin Head-Gordon

Keyword(s):

Electric Fields ◽

Density Functional ◽

Basis Set ◽

Equilibrium Geometry ◽

Density Functionals ◽

Functional Theory ◽

First Response ◽

Complete Basis Set ◽

Static polarizabilities are the first response of the electron density to electric fields, and are therefore important for predicting intermolecular and molecule-field interactions. They also offer a global measure of the accuracy of the treatment of excited states by density functionals in a formally exact manner. We have developed a database of benchmark static polarizabilities for 132 small species at equilibrium geometry, using coupled cluster theory through triple excitations (extrapolated to the complete basis set limit), for the purpose of developing and assessing density functionals. The performance of 60 popular and recent functionals are also assessed, which indicates that double hybrid functionals perform the best, having RMS errors in the range of 2.5-3.8% . Many hybrid functionals also give quite reasonable estimates with 4-5% RMSE. A few meta-GGAs like mBEEF and MVS yield performance comparable to hybrids, indicating potential for improved excited state predictions relative to typical local functionals. Some recent functionals however are found to be prone to catastrophic failure (possibly as a consequence of overparameterization), indicating a need for caution in applying these.

On the accuracy of density-functional theory exchange-correlation functionals for H bonds in small water clusters: Benchmarks approaching the complete basis set limit

The Journal of Chemical Physics ◽

10.1063/1.2790009 ◽

2007 ◽

Vol 127 (18) ◽

pp. 184104 ◽

Cited By ~ 177

Author(s):

Biswajit Santra ◽

Angelos Michaelides ◽

Matthias Scheffler

Keyword(s):

Density Functional Theory ◽

Density Functional ◽

Water Clusters ◽

Basis Set ◽

Functional Theory ◽

Exchange Correlation ◽

Small Water ◽

Complete Basis ◽

Complete Basis Set ◽

Complete Basis Set Limit

How Accurate Are Static Polarizability Predictions from Density Functional Theory? An Assessment over 132 Species at Equilibrium Geometry

10.26434/chemrxiv.6449693.v2 ◽

2018 ◽

Author(s):

Diptarka Hait ◽

Martin Head-Gordon

Keyword(s):

Electric Fields ◽

Density Functional ◽

Basis Set ◽

Equilibrium Geometry ◽

Density Functionals ◽

Functional Theory ◽

First Response ◽

Complete Basis Set ◽

Static polarizabilities are the first response of the electron density to electric fields, and are therefore important for predicting intermolecular and molecule-field interactions. They also offer a global measure of the accuracy of the treatment of excited states by density functionals in a formally exact manner. We have developed a database of benchmark static polarizabilities for 132 small species at equilibrium geometry, using coupled cluster theory through triple excitations (extrapolated to the complete basis set limit), for the purpose of developing and assessing density functionals. The performance of 60 popular and recent functionals are also assessed, which indicates that double hybrid functionals perform the best, having RMS errors in the range of 2.5-3.8% . Many hybrid functionals also give quite reasonable estimates with 4-5% RMSE. A few meta-GGAs like mBEEF and MVS yield performance comparable to hybrids, indicating potential for improved excited state predictions relative to typical local functionals. Some recent functionals however are found to be prone to catastrophic failure (possibly as a consequence of overparameterization), indicating a need for caution in applying these.

How Accurate Are Static Polarizability Predictions from Density Functional Theory? An Assessment over 132 Species at Equilibrium Geometry

10.26434/chemrxiv.6449693.v1 ◽

2018 ◽

Author(s):

Diptarka Hait ◽

Martin Head-Gordon

Keyword(s):

Electric Fields ◽

Density Functional ◽

Basis Set ◽

Equilibrium Geometry ◽

Density Functionals ◽

Functional Theory ◽

First Response ◽

Complete Basis Set ◽

Static polarizabilities are the first response of the electron density to electric fields, and are therefore important for predicting intermolecular and molecule-field interactions. They also offer a global measure of the accuracy of the treatment of excited states by density functionals in a formally exact manner. We have developed a database of benchmark static polarizabilities for 132 small species at equilibrium geometry, using coupled cluster theory through triple excitations (extrapolated to the complete basis set limit), for the purpose of developing and assessing density functionals. The performance of 56 popular and recent functionals are also assessed, which indicates that double hybrid functionals perform the best, having RMS errors in the range of 2.5-3.8% . Many hybrid functionals also give quite reasonable estimates with 4-5% RMSE. A few meta-GGAs like mBEEF and MVS yield performance comparable to hybrids, indicating potential for improved excited state predictions relative to typical local functionals. Some recent functionals however are found to be prone to catastrophic failure (possibly as a consequence of overparameterization), indicating a need for caution in applying these.

Evaluating Transition Metal Barrier Heights with the Latest Density Functional Theory Exchange–Correlation Functionals: The MOBH35 Benchmark Database

The Journal of Physical Chemistry A ◽

10.1021/acs.jpca.9b01546 ◽

2019 ◽

Vol 123 (17) ◽

pp. 3761-3781 ◽

Cited By ~ 24

Author(s):

Mark A. Iron ◽

Trevor Janes

Keyword(s):

Density Functional Theory ◽

Transition Metal ◽

Density Functional ◽

Functional Theory ◽

Exchange Correlation ◽

Barrier Heights ◽

Benchmark Database ◽

Metal Barrier

SVECV-F12: A Composite Scheme for an Accurate and Cost Effective Evaluation of Reaction Barriers. I. Benchmarking Using the HTBH38/08 and NHTBH38/08 Barrier Heights Databases

10.26434/chemrxiv.11770023.v1 ◽

2020 ◽

Author(s):

Oscar Ventura

Keyword(s):

Density Functional ◽

Cost Effective ◽

Basis Set ◽

Barrier Heights ◽

Composite Methods ◽

Complete Basis Set ◽

Complete Set ◽

Reaction Barriers ◽

Better Than

A simple version of a composite scheme is described, based on a combination of density functional geometry and frequencies evaluation, valence energies obtained using the CCSD(T)-f12 method extrapolated to the complete basis set limit, and core-valence correlation corrections employing the MP2 method. The procedure was applied to the 38 reactions in Truhlar’s HTBH38/08 and NHTBH38/08 databases. Mean unsigned deviation (MUD) for the complete set of 68 independent barriers is 0.43 kcal mol-1, compared to 1.37 kcal/mol for G4 and 1.69 kcal/mol for the dispersioncorrected M06-2X method. Its accuracy is also better that that of other calculations using composite methods of similar cost. The MUD of the new scheme on the barriers in the DBH24/08 subset (12 out of the 38 reactions in both other sets) is 0.31 kcal mol-1, better than that obtained at the expensive CCSD(T,full)/aug-cc-pCV(T+d)Z level (0.46 kcal mol-1) and comparable to the most exact (and costly) Wn calculations (MUD=0.14 kcal mol-1). The maximum unsigned deviation (MaxUD) of the new method for all the reactions studied is 1.71 kcal/mol. G4 and M06-2X, on the other side, exhibit MaxUDs of 6.7 and 8.4 kcal/mol respectively

SVECV-F12: A Composite Scheme for an Accurate and Cost Effective Evaluation of Reaction Barriers. I. Benchmarking Using the HTBH38/08 and NHTBH38/08 Barrier Heights Databases

10.26434/chemrxiv.11770023 ◽

2020 ◽

Author(s):

Oscar Ventura

Keyword(s):

Density Functional ◽

Cost Effective ◽

Basis Set ◽

Barrier Heights ◽

Composite Methods ◽

Complete Basis Set ◽

Complete Set ◽

Reaction Barriers ◽

Better Than

A simple version of a composite scheme is described, based on a combination of density functional geometry and frequencies evaluation, valence energies obtained using the CCSD(T)-f12 method extrapolated to the complete basis set limit, and core-valence correlation corrections employing the MP2 method. The procedure was applied to the 38 reactions in Truhlar’s HTBH38/08 and NHTBH38/08 databases. Mean unsigned deviation (MUD) for the complete set of 68 independent barriers is 0.43 kcal mol-1, compared to 1.37 kcal/mol for G4 and 1.69 kcal/mol for the dispersioncorrected M06-2X method. Its accuracy is also better that that of other calculations using composite methods of similar cost. The MUD of the new scheme on the barriers in the DBH24/08 subset (12 out of the 38 reactions in both other sets) is 0.31 kcal mol-1, better than that obtained at the expensive CCSD(T,full)/aug-cc-pCV(T+d)Z level (0.46 kcal mol-1) and comparable to the most exact (and costly) Wn calculations (MUD=0.14 kcal mol-1). The maximum unsigned deviation (MaxUD) of the new method for all the reactions studied is 1.71 kcal/mol. G4 and M06-2X, on the other side, exhibit MaxUDs of 6.7 and 8.4 kcal/mol respectively

SVECV-f12: benchmark of a composite scheme for accurate and cost effective evaluation of reaction barriers.

10.26434/chemrxiv.11770023.v2 ◽

2021 ◽

Author(s):

Oscar Ventura ◽

Martina Kieninger ◽

Aline Katz ◽

Mauricio Vega-Teijido ◽

Marc E. Segovia ◽

...

Keyword(s):

Atmospheric Chemistry ◽

Density Functional ◽

Cost Effective ◽

The Other ◽

Basis Set ◽

Barrier Heights ◽

Composite Methods ◽

Complete Basis Set ◽

Reaction Barriers

A simple composite scheme is presented, based on a combination of density functional geometry and frequencies evaluation, valence energies obtained using the CCSD(T)-f12 method extrapolated to the complete basis set limit, and core-valence correlation corrections employing the MP2 method. The procedure was applied to the 38 reactions in Truhlar’s HTBH38/08 and NHTBH38/08 databases and the errors in the barriers with respect to their best values are presented. Mean unsigned deviation (MUD) for the complete set of 68 independent barriers is 0.40 kcal mol-1 , compared to 1.31 kcal/mol for G4 and 1.62 kcal/mol for the dispersion-corrected M06- 2X method. The accuracy of the procedure is also better that that of other calculations using composite methods of similar cost. The MUD of the new scheme on the barriers in the DBH24/08 subset (12 out of the 38 reactions in the other two sets) is 0.27 kcal mol-1 , better than that obtained at the expensive CCSD(T,full)/aug-cc-pCV(T+d)Z level (0.46 kcal mol-1 ) and comparable to the 2 most exact (and costly) Wn calculations (MUD=0.14 kcal mol-1 ). The maximum unsigned deviation (MaxUD) for all the reactions studied is 0.99 kcal/mol. G4 and M06-2X, on the other side, exhibit MaxUDs of 6.7 and 8.0 kcal/mol respectively. The method was further tested against a subset of the reactions in the databases, for which the geometry and energies of all species were determined at the much more demanding CCSD(T)-F12//pVQZ-F12 level. These results showed that Truhlar’s calculations in this subset are off the best values by a considerable amount, with an rmse of 0.56 kcal/mol. As a consequence, a new dataset of barrier heights, SV20, is presented. The SVECV-F12 procedure on this SV20 database results in rmse and MUD values of only 0.21 and 0.16 kcal/mol. The possible residual errors introduced by the approximations used for each component of the method are tested against more sophisticated calculations and shown to be accurate enough to obtain barriers well under the chemical precision limit at a reasonable cost for molecules of interest in atmospheric chemistry.