Rydberg states of ZnAr complex

<i>Ab initio</i> potential energy curves (PECs) of electronic states of ZnAr complex are calculated up to Rydberg state correlating with the (4s6s)1S0 asymptote of Zn atom. Analysis of various sources of errors of presented calculations is performed including finite basis set size, deficiencies in inclusion of the electron correlation and relativistic effects, and size-inconsistency errors of the multireference second-order perturbation theory. In particular, it is emphasised that the inclusion of the midbond bases substantially improves the convergence rate of the binding energies with respect to the basis set size not only for the van der Waals ground state of ZnAr complex, but also it is the case for the excited states including the Rydberg ones. Wherever it is possible, the comparison with the experimental data and other theoretical results is presented. Properties of the double-well PECs of the Σ Rydberg states are interpreted within the simplified theory, in which, the appearance of the energy barrier and, partially, of the outer well originates from the low-energy scattering of the Rydberg electron on the Ar atom.