Ab initio computations close to the one‐particle basis set limit on the weakly bound van der Waals complexes benzene–neon and benzene–argon

The equilibrium geometries and binding energies of the van der Waals (vdW) complexes benzene–neon and benzene–argon have been calculated at the level of second‐order Mo/ller–Plesset perturbation theory (MP2). Terms linear in the interelectronic distances r12 were used in the MP2 treatment to converge fast to the one‐particle basis set limit. This new method, MP2‐R12 as implemented in the sore program, was applied with high quality basis sets derived from Dunning’s aug‐cc‐pVXZ (X=D,T,Q,5) sets. In reward of the efforts to reach the basis set limit, it is found that the calculated binding energies for the vdW complexes were computed virtually free of a basis set superposition error (BSSE). The key MP2‐R12 results are De=154 cm−1 and re=3.32 A for benzene–neon and De=553 cm−1 and re=3.41 A for benzene–argon. The permanent dipole moments of the vdW complexes have been computed by finite field perturbation theory. Coupled‐cluster calculations of type CCSD(T), although performed with considerably smaller basis ...

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