Transition state localization by a density functional method. Applications to isomerization and symmetry-forbidden reactions

Summary

A new transition state algorithm incorporated into the density functional code deMon, has been used to study thetrans →cis-hydroxymethylene andtrans-hydroxymethylene → formaldehyde isomerization processes and to localize the transition state for the decomposition of 1,3-diazacyclobutane to methyleneimine. Calculations have been performed using both local (LSD) and nonlocal spin density (NLSD) gradient-corrected approximations. Two different basis sets of small and large size have been used for the study in order to analyze the effect of the basis set dimension other than that of the nonlocal corrections on the activation energy barrier value. The results seem to confirm that density functional methods can be considered practical and reliable tools for the localization of transition states.