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Adiabatic connection method for X − + RX nucleophilic substitution reactions (X = F, Cl)
Author(s) -
Kormos Bethany L.,
Cramer Christopher J.
Publication year - 2002
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.548
Subject(s) - chemistry , nucleophilic substitution , heterolysis , nucleophile , adiabatic process , fluorine , halide , chlorine , computational chemistry , connection (principal bundle) , substitution (logic) , alkyl , medicinal chemistry , thermodynamics , organic chemistry , physics , structural engineering , computer science , engineering , programming language , catalysis
A modified Perdew–Wang one‐parameter hybrid density functional ( m PW1N) was developed for nucleophilic substitution reactions by optimizing the fraction of exact exchange in v PW1PW91/6–31+G(d). Activation energies for 20 identity nucleophilic substitution and alkyl halide heterolysis reactions involving fluorine and chlorine were compared to values computed at the MCG3//MC‐QCISD level to arrive at an optimal value of 40.6% HF exchange in m PW1N. This choice also leads to improved transition‐state geometries over the training set. Results from m PW1N are compared with those from other common DFT methods, and some sources of error are explored. Copyright © 2002 John Wiley & Sons, Ltd.
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