Limitations of current density functional theories for the description of partial π-bond breaking

Cheol Ho Choi; Miklos Kertesz; Alfred Karpfen

doi:10.1016/S0009-2614(97)00806-3

Limitations of current density functional theories for the description of partial π-bond breaking

Cheol Ho Choi, Miklos Kertesz, Alfred Karpfen

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Abstract

It is shown on the example of the torsional potential of butadiene, that several density functionals including gradient corrected non-local functionals exhibit an intrinsic error that leads to the overestimation of rotational barriers due to partial π-bond breaking. This problem occurs for all functionals investigated including SVWN, BLYP, B3LYP, BPL and BP86 and is independent of the basis set. The hybrid exchange functional (B3) is slightly better than the others. These errors are absent for torsional potentials around single bonds, such as in 1-butene and indicates that the problem may be related to the overestimation of conjugation energy.

Original language	English
Pages (from-to)	266-268
Number of pages	3
Journal	Chemical Physics Letters
Volume	276
Issue number	3-4
DOIs	https://doi.org/10.1016/S0009-2614(97)00806-3
State	Published - 19 Sep 1997

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title = "Limitations of current density functional theories for the description of partial π-bond breaking",

abstract = "It is shown on the example of the torsional potential of butadiene, that several density functionals including gradient corrected non-local functionals exhibit an intrinsic error that leads to the overestimation of rotational barriers due to partial π-bond breaking. This problem occurs for all functionals investigated including SVWN, BLYP, B3LYP, BPL and BP86 and is independent of the basis set. The hybrid exchange functional (B3) is slightly better than the others. These errors are absent for torsional potentials around single bonds, such as in 1-butene and indicates that the problem may be related to the overestimation of conjugation energy.",

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T1 - Limitations of current density functional theories for the description of partial π-bond breaking

AU - Choi, Cheol Ho

AU - Kertesz, Miklos

AU - Karpfen, Alfred

PY - 1997/9/19

Y1 - 1997/9/19

N2 - It is shown on the example of the torsional potential of butadiene, that several density functionals including gradient corrected non-local functionals exhibit an intrinsic error that leads to the overestimation of rotational barriers due to partial π-bond breaking. This problem occurs for all functionals investigated including SVWN, BLYP, B3LYP, BPL and BP86 and is independent of the basis set. The hybrid exchange functional (B3) is slightly better than the others. These errors are absent for torsional potentials around single bonds, such as in 1-butene and indicates that the problem may be related to the overestimation of conjugation energy.

AB - It is shown on the example of the torsional potential of butadiene, that several density functionals including gradient corrected non-local functionals exhibit an intrinsic error that leads to the overestimation of rotational barriers due to partial π-bond breaking. This problem occurs for all functionals investigated including SVWN, BLYP, B3LYP, BPL and BP86 and is independent of the basis set. The hybrid exchange functional (B3) is slightly better than the others. These errors are absent for torsional potentials around single bonds, such as in 1-butene and indicates that the problem may be related to the overestimation of conjugation energy.

UR - https://www.scopus.com/pages/publications/0031578415

U2 - 10.1016/S0009-2614(97)00806-3

DO - 10.1016/S0009-2614(97)00806-3

M3 - Article

AN - SCOPUS:0031578415

SN - 0009-2614

VL - 276

SP - 266

EP - 268

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 3-4

ER -

Limitations of current density functional theories for the description of partial π-bond breaking

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