Range-separated hybrid functionals for mixed dimensional heterojunctions: Application to phthalocyanines/MoS2

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.

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Minimally Empirical Double Hybrid Functionals Trained Against the GMTKN55 Database: revDSD-PBEP86-D4, revDOD-PBE-D4, and DOD-SCAN-D4

10.26434/chemrxiv.7903388.v2 ◽

2019 ◽

Cited By ~ 1

Author(s):

Golokesh Santra ◽

Nitai Sylvetsky ◽

Gershom Martin

Keyword(s):

Substantial Improvement ◽

Viable Alternative ◽

Mean Absolute Deviation ◽

Dispersion Correction ◽

Training Set ◽

Weighted Mean ◽

Absolute Deviation ◽

Hybrid Functionals ◽

Scaling Algorithms

We present a family of minimally empirical double-hybrid DFT functionals parametrized against the very large and diverse GMTKN55 benchmark. The very recently proposed wB97M(2) empirical double hybrid (with 16 empirical parameters) has the lowest WTMAD2 (weighted mean absolute deviation over GMTKN55) ever reported at 2.19 kcal/mol. However, our xrevDSD-PBEP86-D4 functional reaches a statistically equivalent WTMAD2=2.22 kcal/mol, using just a handful of empirical parameters, and the xrevDOD-PBEP86-D4 functional reaches 2.25 kcal/mol with just opposite-spin MP2 correlation, making it amenable to reduced-scaling algorithms. In general, the D4 empirical dispersion correction is clearly superior to D3BJ. If one eschews dispersion corrections of any kind, noDispSD-SCAN offers a viable alternative. Parametrization over the entire GMTKN55 dataset yields substantial improvement over the small training set previously employed in the DSD papers.

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Minimally Empirical Double Hybrid Functionals Trained Against the GMTKN55 Database: revDSD-PBEP86-D4, revDOD-PBE-D4, and DOD-SCAN-D4

10.26434/chemrxiv.7903388.v1 ◽

2019 ◽

Author(s):

Golokesh Santra ◽

Nitai Sylvetsky ◽

Gershom Martin

Keyword(s):

Substantial Improvement ◽

Viable Alternative ◽

Mean Absolute Deviation ◽

Dispersion Correction ◽

Training Set ◽

Weighted Mean ◽

Absolute Deviation ◽

Hybrid Functionals ◽

Scaling Algorithms

We present a family of minimally empirical double-hybrid DFT functionals parametrized against the very large and diverse GMTKN55 benchmark. The very recently proposed wB97M(2) empirical double hybrid (with 16 empirical parameters) has the lowest WTMAD2 (weighted mean absolute deviation over GMTKN55) ever reported at 2.19 kcal/mol. However, our xrevDSD-PBEP86-D4 functional reaches a statistically equivalent WTMAD2=2.22 kcal/mol, using just a handful of empirical parameters, and the xrevDOD-PBEP86-D4 functional reaches 2.25 kcal/mol with just opposite-spin MP2 correlation, making it amenable to reduced-scaling algorithms. In general, the D4 empirical dispersion correction is clearly superior to D3BJ. If one eschews dispersion corrections of any kind, noDispSD-SCAN offers a viable alternative. Parametrization over the entire GMTKN55 dataset yields substantial improvement over the small training set previously employed in the DSD papers.

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Accuracy of electron densities obtained via Koopmans-compliant hybrid functionals

Physical Review Materials ◽

10.1103/physrevmaterials.2.040801 ◽

2018 ◽

Vol 2 (4) ◽

Cited By ~ 8

Author(s):

A. R. Elmaslmane ◽

J. Wetherell ◽

M. J. P. Hodgson ◽

K. P. McKenna ◽

R. W. Godby

Keyword(s):

Electron Densities ◽

Hybrid Functionals

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Computing with DFT Band Offsets at Semiconductor Interfaces: A Comparison of Two Methods

Nanomaterials ◽

10.3390/nano11061581 ◽

2021 ◽

Vol 11 (6) ◽

pp. 1581

Author(s):

José C. Conesa

Keyword(s):

Significant Problem ◽

Band Offsets ◽

Semiconductor Interfaces ◽

Hartree Potential ◽

Hybrid Functionals

Two DFT-based methods using hybrid functionals and plane-averaged profiles of the Hartree potential (individual slabs versus vacuum and alternating slabs of both materials), which are frequently used to predict or estimate the offset between bands at interfaces between two semiconductors, are analyzed in the present work. These methods are compared using several very different semiconductor pairs, and the conclusions about the advantages of each method are discussed. Overall, the alternating slabs method is recommended in those cases where epitaxial mismatch does not represent a significant problem.

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