The performance of computational techniques in locating the charge separated intermediates in organocatalytic transformations

The formation of zwitterionic adducts between neutral nucleophiles such as NMe(3) and PMe(3) with neutral electrophiles such as methyl vinyl ketone (MVK) has been studied with a wide variety of theoretical methods. It has been found that hybrid density functional methods such as B3LYP are not capable of describing these zwitterionic structures as minima on the potential energy surface. This is also true for combinations of MP2 theory with basis sets lacking diffuse basis functions. The mPW1K hybrid functional, in contrast, correctly describes zwitterionic adducts as true intermediates on the PES. On the basis of this insight, a new version of the G3 compound energy scheme has been developed for the accurate description of zwitterionic structures. It has also been verified that modifications of the B2-PLYP double-hybrid functional are equally capable of the proper description of zwitterionic adducts. The applicability of this latter class of methods to a larger dataset involving combinations of different nucleophiles and electrophiles has been documented.