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

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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.

Original languageEnglish
Pages (from-to)558-564
Number of pages7
JournalChemical Physics Letters
Issue number5-6
StatePublished - 4 Oct 1996


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