Abstract
The results of ab initio calculations, using extended Gaussian basis sets and including correlation energy through a variety of means, provide strong support for the Mg(3 pπ,3 pπ 3 P J) · Ar( 3Σ −) electronic-state assignment made by Massick and Breckenridge to spectral features in the resonant two-photon photoionization spectrum of vibrationally cold Mg(3 s,3 pπ 3 P J) · Ar( 3Π) van der Waals complexes. The doubly excited Mg(3 pπ,3 pπ 3 P J) · Ar( 3Σ −) state is found to be much more strongly bound than the singly excited Mg(3 s,3 pπ 3 P J) · Ar( 3Π) state, which, in turn, is much more bound than the Mg(3 s 2 1 S O ) · Ar( 3Σ +) ground state.
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