Abstract
Correlated values of the isomerization energy and barrier for the HNC→HCN reaction are obtained from many-body perturbation theory, including the effects of quadruple excitations. Extended basis sets of better-than-triple-zeta plus double-polarization quality are used, as well as basis sets including counterpoise and bond-centered orbitals. The best of these basis sets is sufficient to account for 84% of the valence correlation energy of HCN. These studies predict an isomerization energy for the HNC→HCN rearrangement to be −15±2 kcal/mole, in disagreement with a recent experimental value of −10.3±1. kcal/mole. Correlated isomerization energies of LiCN→LiNC and BCN→BNC are obtained in bases of double-zeta plus polarization quality. In all cases, correlation stabilizes the cyanide isomer more than the isocyanide. Trends in the series R–NC⇄RCN for R=H, Li, and B are discussed.
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