The performance of B3-LYP density functional theory in describing S(N)2 reactions at saturated carbon

被引：115

作者：

Glukhovtsev, MN

Bach, RD

Pross, A

Radom, L

机构：

[1] UNIV DELAWARE, DEPT CHEM, NEWARK, DE 19716 USA

[2] UNIV SYDNEY, SCH CHEM, SYDNEY, NSW 2006, AUSTRALIA

[3] BEN GURION UNIV NEGEV, DEPT CHEM, BEER SHEVA, ISRAEL

[4] AUSTRALIAN NATL UNIV, RES SCH CHEM, CANBERRA, ACT 0200, AUSTRALIA

来源：

CHEMICAL PHYSICS LETTERS | 1996年 / 260卷 / 5-6期

关键词：

D O I：

10.1016/0009-2614(96)00923-2

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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(N)2 reactions of Cl- + CH3Cl and Cl- + CH3Br has been examined in detail. Reasonable values of the complexation energies (Delta H-comp) for the ion-molecule complexes formed in these reactions are obtained. However, the overall (Delta H-ovr(#)) and central (Delta H-cent(#)) barriers for these reactions calculated using the B3-LYP functional are significantly underestimated when compared with G2(-t) or experimental results. This implies that the B3-LYP energies for the Cl(H3CCl- (D-3h) and Cl(H3CBr- (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.

引用

页码：558 / 564

页数：7

共 35 条

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