Highly accurate equilibrium structure of the C2h symmetric N1‐to‐O2 hydrogen‐bonded uracil‐dimer.

Abstract: The highly accurate ab initio equilibrium geometry of the hydrogen‐bonded uracil dimer is derived using a composite geometry extrapolation scheme based on all‐electron, complete basis set extrapolated Møller–Plesset perturbation theory using the jun‐pwCV[T,Q]Z basis sets combined with a valence CCSD(T)/cc‐pVTZ high‐level correction. Geometrical changes on dimerization are discussed and the performance of the several density functional approximations (among others SCAN, ωB97M‐V, DSD‐PBEP86‐D3(BJ), and DSD‐PBEP86‐NL) is evaluated. Orbital‐optimized MP2.5 is discussed as a reduced‐cost alternative to the CCSD(T) gradient in the composite scheme. A new reference interaction energy is calculated with explicitly correlated F12‐CCSD(T). [ABSTRACT FROM AUTHOR]