The performance of B3-LYP density functional theory in describing SN2 reactions at saturated carbon

Mikhail N. Glukhovtsev; Robert D. Bach; Addy Pross; Leo Radom

doi:10.1016/0009-2614(96)00923-2

The performance of B3-LYP density functional theory in describing S_N2 reactions at saturated carbon

Mikhail N. Glukhovtsev, Robert D. Bach, Addy Pross, Leo Radom

Department of Chemistry

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Abstract

The performance of the B3-LYP variant of density functional theory when used in conjunction with the 6-31G(d) and 6-311 + G(3df, 2p) basis sets in describing the prototypical gas-phase S_N2 reactions of Cl^- + CH₃Cl and Cl^- + CH₃Br has been examined in detail. Reasonable values of the complexation energies (ΔH_comp) for the ion-molecule complexes formed in these reactions are obtained. However, the overall (ΔH^#_ovr) and central (ΔH^#_cent) barriers for these reactions calculated using the B3-LYP functional are significantly underestimated when compared with G2(+) or experimental results. This implies that the B3-LYP energies for the Cl(H₃C)Cl^- (D_3h) and Cl(H₃C)Br^- (C_3v) transition structures are relatively too low. The B3-LYP errors appear to be systematic, with similar errors being found for corresponding quantities for the two reactions examined.

Original language	English
Pages (from-to)	558-564
Number of pages	7
Journal	Chemical Physics Letters
Volume	260
Issue number	5-6
DOIs	https://doi.org/10.1016/0009-2614(96)00923-2
State	Published - 4 Oct 1996

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General Physics and Astronomy
Physical and Theoretical Chemistry

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title = "The performance of B3-LYP density functional theory in describing SN2 reactions at saturated carbon",

abstract = "The performance of the B3-LYP variant of density functional theory when used in conjunction with the 6-31G(d) and 6-311 + G(3df, 2p) basis sets in describing the prototypical gas-phase SN2 reactions of Cl- + CH3Cl and Cl- + CH3Br has been examined in detail. Reasonable values of the complexation energies (ΔHcomp) for the ion-molecule complexes formed in these reactions are obtained. However, the overall (ΔH#ovr) and central (ΔH#cent) barriers for these reactions calculated using the B3-LYP functional are significantly underestimated when compared with G2(+) or experimental results. This implies that the B3-LYP energies for the Cl(H3C)Cl- (D3h) and Cl(H3C)Br- (C3v) transition structures are relatively too low. The B3-LYP errors appear to be systematic, with similar errors being found for corresponding quantities for the two reactions examined.",

author = "Glukhovtsev, {Mikhail N.} and Bach, {Robert D.} and Addy Pross and Leo Radom",

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T1 - The performance of B3-LYP density functional theory in describing SN2 reactions at saturated carbon

AU - Glukhovtsev, Mikhail N.

AU - Bach, Robert D.

AU - Pross, Addy

AU - Radom, Leo

PY - 1996/10/4

Y1 - 1996/10/4

N2 - The performance of the B3-LYP variant of density functional theory when used in conjunction with the 6-31G(d) and 6-311 + G(3df, 2p) basis sets in describing the prototypical gas-phase SN2 reactions of Cl- + CH3Cl and Cl- + CH3Br has been examined in detail. Reasonable values of the complexation energies (ΔHcomp) for the ion-molecule complexes formed in these reactions are obtained. However, the overall (ΔH#ovr) and central (ΔH#cent) barriers for these reactions calculated using the B3-LYP functional are significantly underestimated when compared with G2(+) or experimental results. This implies that the B3-LYP energies for the Cl(H3C)Cl- (D3h) and Cl(H3C)Br- (C3v) transition structures are relatively too low. The B3-LYP errors appear to be systematic, with similar errors being found for corresponding quantities for the two reactions examined.

AB - The performance of the B3-LYP variant of density functional theory when used in conjunction with the 6-31G(d) and 6-311 + G(3df, 2p) basis sets in describing the prototypical gas-phase SN2 reactions of Cl- + CH3Cl and Cl- + CH3Br has been examined in detail. Reasonable values of the complexation energies (ΔHcomp) for the ion-molecule complexes formed in these reactions are obtained. However, the overall (ΔH#ovr) and central (ΔH#cent) barriers for these reactions calculated using the B3-LYP functional are significantly underestimated when compared with G2(+) or experimental results. This implies that the B3-LYP energies for the Cl(H3C)Cl- (D3h) and Cl(H3C)Br- (C3v) transition structures are relatively too low. The B3-LYP errors appear to be systematic, with similar errors being found for corresponding quantities for the two reactions examined.

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JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 5-6

ER -

The performance of B3-LYP density functional theory in describing S_N2 reactions at saturated carbon

Abstract

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