dorsal/arxiv
View SchemaAssessment of Various Density Functionals and Basis Sets for the Calculation of Molecular Anharmonic Force Fields
| Authors | A. Daniel Boese, Wim Klopper, Jan M. L. Martin |
|---|---|
| Categories | |
| ArXiv ID | physics/0503180 |
| URL | https://arxiv.org/abs/physics/0503180 |
| DOI | 10.1002/qua.20644 |
| Journal | International Journal of Quantum Chemistry 104, 830-845 (2005) |
Abstract
In a previous contribution (Mol. Phys. {\bf 103}, xxxx, 2005), we established the suitability of density functional theory (DFT) for the calculation of molecular anharmonic force fields. In the present work, we have assessed a wide variety of basis sets and exchange-correlation functionals for harmonic and fundamental frequencies, equilibrium and ground-state rotational constants, and thermodynamic functions beyond the RRHO (rigid rotor-harmonic oscillator) approximation. The fairly good performance of double-zeta plus polarization basis sets for frequencies results from an error compensation between basis set incompleteness and the intrinsic error of exchange-correlation functionals. Triple-zeta plus polarization basis sets are recommended, with an additional high-exponent $d$ function on second-row atoms. All conventional hybrid GGA functionals perform about equally well: high-exchange hybrid GGA and meta-GGA functionals designed for kinetics yield poor results, with the exception of of the very recently developed BMK functional which takes a middle position along with the HCTH/407 (second generation GGA) and TPSS (meta-GGA) functionals. MP2 performs similarly to these functionals but is inferior to hybrid GGAs such as B3LYP and B97-1.
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"abstract": "In a previous contribution (Mol. Phys. {\\bf 103}, xxxx, 2005), we established\nthe suitability of density functional theory (DFT) for the calculation of\nmolecular anharmonic force fields. In the present work, we have assessed a wide\nvariety of basis sets and exchange-correlation functionals for harmonic and\nfundamental frequencies, equilibrium and ground-state rotational constants, and\nthermodynamic functions beyond the RRHO (rigid rotor-harmonic oscillator)\napproximation. The fairly good performance of double-zeta plus polarization\nbasis sets for frequencies results from an error compensation between basis set\nincompleteness and the intrinsic error of exchange-correlation functionals.\nTriple-zeta plus polarization basis sets are recommended, with an additional\nhigh-exponent $d$ function on second-row atoms. All conventional hybrid GGA\nfunctionals perform about equally well: high-exchange hybrid GGA and meta-GGA\nfunctionals designed for kinetics yield poor results, with the exception of of\nthe very recently developed BMK functional which takes a middle position along\nwith the HCTH/407 (second generation GGA) and TPSS (meta-GGA) functionals. MP2\nperforms similarly to these functionals but is inferior to hybrid GGAs such as\nB3LYP and B97-1.",
"arxiv_id": "physics/0503180",
"authors": [
"A. Daniel Boese",
"Wim Klopper",
"Jan M. L. Martin"
],
"categories": [
"physics.chem-ph",
"physics.comp-ph"
],
"doi": "10.1002/qua.20644",
"journal_ref": "International Journal of Quantum Chemistry 104, 830-845 (2005)",
"title": "Assessment of Various Density Functionals and Basis Sets for the Calculation of Molecular Anharmonic Force Fields",
"url": "https://arxiv.org/abs/physics/0503180"
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