The article presents the experimental and theoretical analysis of the ArICl(IP, vIP, nIP) states population and decay at energies lower than the ArICl( E, vE =0, nE) dissociation limit (IP = E0+, , β1), vIP = 0, 1, nIP are quantum numbers of the van der Waals (vdW) modes). We have measured excitation spectra of the ArICl( E, vE=0,1, nE → X, vX, nX) and ArICl( β,0, n β → A and/or luminescence as well as luminescence spectra themselves. To construct potential energy surfaces (PES's) for valence, A1, 2, and ion-pair, E, β, and electronic states of the complex, we utilized the intermolecular diatomic-in-molecule perturbation theory first order (IDIM PT1) method. Experimental and calculated spectroscopic characteristics of the T-shaped ArICl valence and E, β states agree well. The ArICl( ) state PES has no vdW levels in the T-shaped configuration, and collinear ArICl( ) binding energy is larger than that of T-shaped ArICl( β) state. We calculated vibrational state energies and the ArICl(IP → valence states) luminescence excitation spectra and luminescence spectra themselves using the Heidelberg MCTDH code. Comparison of the experimental and calculated excitation spectra shows that the latter describe their principal features. The bound-bound ArICl( E,0, nE → X and β,0, n β → A) parts of experimental luminescence spectra are described by calculated spectra adequately, and bound-free ArICl( E,0, nE → X, → ) not since bound-free transitions occur to repulsive parts of the ArICl( X, PES's which we cannot describe accurately.
