Performance of PNOF3 for reactivity studies: X[BO] and X[CN]isomerization reactions (X = H, Li) as a case study

Abstract

Natural Orbital Functional Theory in its PNOF3 implementation is used to investigate the potential energy surfaces of four isomerization reactions: (i) BOH to HBO; (ii) BOLi to LiBO; (iii) CNH to HCN; and (iv) CNLi to LiCN. These reactions are taken as a case study to illustrate the potentiality of PNOF3 to yield the correct topology for reactions sensible to electron correlation. The perfomance of PNOF3 to yield accurate reaction barriers and isomerization energies is also discussed. We have found that PNOF3 shows promising behaviour in the description of these delicate PESs, and yield the correct trends in isomerization energies and reaction barriers, although the latter trends tend to be somewhat lower than the ones calculated at highly correlated levels of theory. The present results show that PNOF3 can give a balanced description of electron correlation in both equilibrium and non-equilibrium structures.