Characterization of the potential energy surfaces of two small but challenging noncovalent dimers: (P2)2 and (PCCP)2

Abstract

This work characterizes eight stationary points of the P₂ dimer and six stationary points of the PCCP dimer, including a newly identified minimum on both potential energy surfaces. Full geometry optimizations and corresponding harmonic vibrational frequencies were computed with the second-order Moller-Plesset (MP2) electronic structure method and six different basis sets: aug-cc-pVXZ, aug-cc-pV(X+d)Z, and aug-cc-pCVXZ where X = T, Q. A new L-shaped structure with C₂ symmetry is the only minimum for the P₂ dimer at the MP2 level of theory with these basis sets. The previously reported parallel-slipped sturcture with C_2h symmetry and a newly identified cross configuration with D₂ symmetry are the only minima for the PCCP dimer. Single point energies were also computed using the canonical MP2 and CCSD(T) methods as well as the explicitly correlated MP2-F12 and CCSD(T)-F12 methods and the aug-cc-pVXZ (X = D, T, Q, 5) basis sets. The energetics obtained with the explicitly correlated methods were very similar to the canonical results for the larger basis sets. Extrapolations were performed to estimate the complete basis set (CBS) limit MP2 and CCSD(T) binding energies. MP2 and MP2-F12 significantly overbind the P₂ and PCCP dimers relative to the CCSD(T) and CCSD(T)-F12 binding energies by as much as 1.5 kcal mol^-1 for the former and 5.0 kcal mol^-1 for the latter at the CBS limit. The dominant attractive component of the interaction energy for each dimer configuration was dispersion according to several symmetry-adapted perturbation theory analyses.