The formic acid molecule, its dimers, and its molecular crystal are adopted as test systems to compare results obtained with plane wave (PW) basis sets and norm- conserving pseudopotentials to all- electron Gaussian- type orbital (GTO) calculations. The CPMD and CRYSTAL06 codes, respectively, are applied with the PBE, PW91, and BLYP density functionals. Hydrogen bonding is the leading interaction in the dimers and the crystal. In the latter, dispersive and weak C - H center dot center dot center dot O interactions are also relevant. Irrespective of the adopted functional, for all considered structures PW and GTO results converge smoothly as a function of the quality of the adopted basis sets to the same values for structures, energies of interaction, and harmonic vibrational features. To achieve a high level of mutual agreement the use of GTO basis sets of at least of triple- zeta quality including one set of polarization functions and PW basis sets with a kinetic energy cutoff higher than 110 Ry is recommended. Pros and cons of both approaches for studying molecular crystals are also discussed. (C) 2007 American Institute of Physics. [DOI: 10.1063/ 1.2790019]

Tosoni, S., Tuma, C., Sauer, J., Civalleri, B., Ugliengo, P. (2007). A comparison between plane wave and Gaussian-type orbital basis sets for hydrogen bonded systems: Formic acid as a test case. THE JOURNAL OF CHEMICAL PHYSICS, 127(15) [10.1063/1.2790019].

A comparison between plane wave and Gaussian-type orbital basis sets for hydrogen bonded systems: Formic acid as a test case

Tosoni, S;
2007

Abstract

The formic acid molecule, its dimers, and its molecular crystal are adopted as test systems to compare results obtained with plane wave (PW) basis sets and norm- conserving pseudopotentials to all- electron Gaussian- type orbital (GTO) calculations. The CPMD and CRYSTAL06 codes, respectively, are applied with the PBE, PW91, and BLYP density functionals. Hydrogen bonding is the leading interaction in the dimers and the crystal. In the latter, dispersive and weak C - H center dot center dot center dot O interactions are also relevant. Irrespective of the adopted functional, for all considered structures PW and GTO results converge smoothly as a function of the quality of the adopted basis sets to the same values for structures, energies of interaction, and harmonic vibrational features. To achieve a high level of mutual agreement the use of GTO basis sets of at least of triple- zeta quality including one set of polarization functions and PW basis sets with a kinetic energy cutoff higher than 110 Ry is recommended. Pros and cons of both approaches for studying molecular crystals are also discussed. (C) 2007 American Institute of Physics. [DOI: 10.1063/ 1.2790019]
Articolo in rivista - Articolo scientifico
density-functional theory; electronic-structure calculations; initio; molecular-dynamics; pseudo-potential errors; ab-initio; correlation-energy; ultrasoft pseudopotentials; vibrational frequencies; exact exchange; complexes
English
2007
127
15
154102
none
Tosoni, S., Tuma, C., Sauer, J., Civalleri, B., Ugliengo, P. (2007). A comparison between plane wave and Gaussian-type orbital basis sets for hydrogen bonded systems: Formic acid as a test case. THE JOURNAL OF CHEMICAL PHYSICS, 127(15) [10.1063/1.2790019].
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/197686
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