Performance of density functionals for first row transition metal systems

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Performance of density functionals for first row transition metal systems. / Jensen, Kasper; Roos, Björn; Ryde, Ulf.

I: Journal of Chemical Physics, Vol. 126, Nr. 1, 014103, 2007.

Forskningsoutput: TidskriftsbidragArtikel i vetenskaplig tidskrift

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TY - JOUR

T1 - Performance of density functionals for first row transition metal systems

AU - Jensen, Kasper

AU - Roos, Björn

AU - Ryde, Ulf

N1 - The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)

PY - 2007

Y1 - 2007

N2 - This article investigates the performance of five commonly used density functionals, B3LYP, BP86, PBE0, PBE, and BLYP, for studying diatomic molecules consisting of a first row transition metal bonded to H, F, Cl, Br, N, C, O, or S. Results have been compared with experiment wherever possible. Open-shell configurations are found more often in the order PBE0 > B3LYP > PBE similar to BP86 > BLYP. However, on average, 58 of 63 spins are correctly predicted by any functional, with only small differences. BP86 and PBE are slightly better for obtaining geometries, with errors of only 0.020 A. Hybrid functionals tend to overestimate bond lengths by a few picometers and underestimate bond strengths by favoring open shells. Nonhybrid functionals usually overestimate bond energies. All functionals exhibit similar errors in bond energies, between 42 and 53 kJ/mol. Late transition metals are found to be better modeled by hybrid functionals, whereas nonhybrid functionals tend to have less of a preference. There are systematic errors in predicting certain properties that could be remedied. BLYP performs the best for ionization potentials studied here, PBE0 the worst. In other cases, errors are similar. Finally, there is a clear tendency for hybrid functionals to give larger dipole moments than nonhybrid functionals. These observations may be helpful in choosing and improving existing functionals for tasks involving transition metals, and for designing new, improved functionals. (c) 2007 American Institute of Physics.

AB - This article investigates the performance of five commonly used density functionals, B3LYP, BP86, PBE0, PBE, and BLYP, for studying diatomic molecules consisting of a first row transition metal bonded to H, F, Cl, Br, N, C, O, or S. Results have been compared with experiment wherever possible. Open-shell configurations are found more often in the order PBE0 > B3LYP > PBE similar to BP86 > BLYP. However, on average, 58 of 63 spins are correctly predicted by any functional, with only small differences. BP86 and PBE are slightly better for obtaining geometries, with errors of only 0.020 A. Hybrid functionals tend to overestimate bond lengths by a few picometers and underestimate bond strengths by favoring open shells. Nonhybrid functionals usually overestimate bond energies. All functionals exhibit similar errors in bond energies, between 42 and 53 kJ/mol. Late transition metals are found to be better modeled by hybrid functionals, whereas nonhybrid functionals tend to have less of a preference. There are systematic errors in predicting certain properties that could be remedied. BLYP performs the best for ionization potentials studied here, PBE0 the worst. In other cases, errors are similar. Finally, there is a clear tendency for hybrid functionals to give larger dipole moments than nonhybrid functionals. These observations may be helpful in choosing and improving existing functionals for tasks involving transition metals, and for designing new, improved functionals. (c) 2007 American Institute of Physics.

U2 - 10.1063/1.2406071

DO - 10.1063/1.2406071

M3 - Article

VL - 126

JO - Journal of Chemical Physics

T2 - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 1

M1 - 014103

ER -