CCSDT(Q)/CBS thermochemistry for the D5h → D10h isomerization in the C10 carbon cluster: Getting the right answer for the right reason

Abstract

The D5h → D10h isomerization in the C10 carbon cluster is investigated at the relativistic, all-electron CCSDT(Q)/CBS level. Previous high-level studies examined this isomerization at the valence CCSD(T)/CBS level. We show that capturing this isomerization energy requires accurate treatment of the CCSD(T)/CBS, post-CCSD(T), core-valence, scalar relativistic, diagonal Born–Oppenheimer, and zero-point vibrational energy components. Combining these components shows that the two structures are practically isoenergetic at 0 K (i.e., the D5h structure is more stable by merely +0.100 kcal mol−1). We also show that computationally economical composite protocols erroneously predict that the D10h structure is energetically more stable at 0 K.