Benchmark test of a dispersion corrected revised Tao–Mo semilocal functional for thermochemistry, kinetics, and noncovalent interactions of molecules and solids

Jana, Subrata; Myneni, Hemanadhan; Śmiga, Szymon; Constantin, Lucian A.; Samal, Prasanjit

doi:10.1063/5.0060538

Cited by 4 publications

(3 citation statements)

References 117 publications

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“…Another reliable meta-GGA semilocal functional was proposed by TM [34] which has been quite successful at providing reasonably accurate estimates of various quantum chemical and solid-state properties [34,40,[58][59][60][61]. The TM and its revised version revTM [40] functionals, use both the meta-GGA ingredients i.e., z = τ W /τ and α.…”

Section: Background Of Methodologiesmentioning

confidence: 99%

Improved electronic structure prediction of chalcopyrite semiconductors from a semilocal density functional based on Pauli kinetic energy enhancement factor

Ghosh¹,

Jana²,

Niranjan³

et al. 2021

J. Phys.: Condens. Matter

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The correct treatment of d electrons is of prime importance in order to predict the electronic properties of the prototype chalcopyrite semiconductors. The effect of d states is linked with the anion displacement parameter u, which in turn influences the bandgap of these systems. Semilocal exchange–correlation functionals which yield good structural properties of semiconductors and insulators often fail to predict reasonable u because of the underestimation of the bandgaps arising from the strong interplay between d electrons. In the present study, we show that the meta-generalized gradient approximation (meta-GGA) obtained from the cuspless hydrogen density (MGGAC) (2019 Phys. Rev. B 100 155140) performs in an improved manner in apprehending the key features of the electronic properties of chalcopyrites, and its bandgaps are comparative to that obtained using state-of-art hybrid methods. Moreover, the present assessment also shows the importance of the Pauli kinetic energy enhancement factor, α = (τ − τ W )/τ unif in describing the d electrons in chalcopyrites. The present study strongly suggests that the MGGAC functional within semilocal approximations can be a better and preferred choice to study the chalcopyrites and other solid-state systems due to its superior performance and significantly low computational cost.

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Section: Background Of Methodologiesmentioning

confidence: 99%

Improved electronic structure prediction of chalcopyrite semiconductors from a semilocal density functional based on Pauli kinetic energy enhancement factor

Ghosh¹,

Jana²,

Niranjan³

et al. 2021

J. Phys.: Condens. Matter

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View full text Add to dashboard Cite

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“…Accurate BDE values are essential not only for estimating the enthalpy of chemical reactions but also for constructing reaction mechanisms, determining thermodynamically favored reaction pathways, and studying reaction kinetics [1–4]. Additionally, BDE's play a critical role in chemistry [5–7], Physics [8, 9], and biology [10–12], as they can be used to estimate the activation energy (a kinetic property) from the reaction enthalpy (a thermodynamic property) [13, 14].…”

Section: Introductionmentioning

confidence: 99%

Bond dissociation energies of the fifth‐row elements (InI): A quantum theoretical benchmark study

Badran,

Hashlamoun,

Nassar

2023

Int J of Quantum Chemistry

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The bond dissociation energies (BDE) of most main‐group elements have been accurately measured. However, the BDE values for heavy elements, particularly those from the fifth period (InI), are still missing or poorly validated. This study aims to identify the most accurate computational methods for calculating BDE values of compounds containing fifth‐row elements, including In, Sn, Sb, Te, and I, with a focus on readily accessible methods in software packages. The investigation involved a benchmark study using density functional theory (DFT), in addition to the 2nd order Møller–Plesset perturbation theory (MP2) and the coupled cluster with single, double, and perturbative triple excitations CCSD(T). The DFT functionals used in the study include APFD, B3LYP, B3LYP‐D3, B3P86, B97‐D3, BHandH, HSEH1PBE, M06‐2X, MN12‐SX, MN15‐L, and TPSSH. The functionals were carefully selected to cover some popular functionals as well as to cover all levels of the Jacob's ladder of DFT accuracy. The computed BDE values were compared with experimental values, and the results were filtered to remove any possible outliers. The statistical errors (MAPE, RMSE, and Pearson's) were then calculated and used to assess the performance of the methods.

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“…Specifically, we extend the energy calculation up to trimers and enable harmonic phonon calculations, which can now be performed utilizing up to dimers. We test the performance of the resulting multimer embedding approach by embedding PBE0+MBD − multimers into periodic PBE+MBD calculations and comparing with explicit periodic PBE0+MBD results utilizing the X23 ,,, benchmark set, which has been extensively used to test and develop methods for molecular crystals. ,− …”

Section: Introductionmentioning

confidence: 99%

Multimer Embedding Approach for Molecular Crystals up to Harmonic Vibrational Properties

Hoja,

List,

Boese

2023

J. Chem. Theory Comput.

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Accurate calculations of molecular crystals are crucial for drug design and crystal engineering. However, periodic high-level density functional calculations using hybrid functionals are often prohibitively expensive for the relevant systems. These expensive periodic calculations can be circumvented by the usage of embedding methods in which, for instance, the periodic calculation is only performed at a lower-cost level and then monomer energies and dimer interactions are replaced by those of the higher-level method. Herein, we extend such a multimer embedding approach to enable energy corrections for trimer interactions and the calculation of harmonic vibrational properties up to the dimer level. We evaluate this approach for the X23 benchmark set of molecular crystals by approximating a periodic hybrid density functional (PBE0+MBD) by embedding multimers into less expensive calculations using a generalized-gradient approximation functional (PBE+MBD). We show that trimer interactions are crucial for accurately approximating lattice energies within 1 kJ/mol and might also be needed for further improvement of lattice constants and hence cell volumes. Finally, the vibrational properties are already very well captured at the monomer and dimer level, making it possible to approximate vibrational free energies at room temperature within 1 kJ/mol.

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Benchmark test of a dispersion corrected revised Tao–Mo semilocal functional for thermochemistry, kinetics, and noncovalent interactions of molecules and solids

Cited by 4 publications

References 117 publications

Improved electronic structure prediction of chalcopyrite semiconductors from a semilocal density functional based on Pauli kinetic energy enhancement factor

Improved electronic structure prediction of chalcopyrite semiconductors from a semilocal density functional based on Pauli kinetic energy enhancement factor

Bond dissociation energies of the fifth‐row elements (InI): A quantum theoretical benchmark study

Multimer Embedding Approach for Molecular Crystals up to Harmonic Vibrational Properties

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