Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 110, Issue 2, Pages 367-378Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp0513216
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The mechanism of the [2+2] cycloaddition reaction of cyclopentyne to ethylene has been studied using the completely renormalized coupled cluster method with singles, doubles, and noniterative triples (CR-CCSD(T)). In agreement with the experimentally observed stereochemistry, the CR-CCSD(T) method favors the concerted pathway involving a [2+1] transition state, whereas the popular CCSD(T) method, which is often regarded as the gold standard of electronic structure theory, and low-order multireference methods support the less probable biradical mechanism. In addition, the CCSD(T) approach produces an erroneous description of some transition states and intermediates, particularly those which have a significant biradical character. The CR-CCSD(T) calculations indicate that the reaction is a highly exothermic (Delta G(r)(298) = -68 kcal/mol), predominantly concerted process with a relatively low activation barrier on the order of 13- 16 kcal/mol which permits its thermal occurrence.
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