The 2s2p(2) D-2 <-- 2s(2)2p P-2 valence transition in the BAr2 cluster is investigated in a collaborative experimental and theoretical study. Laser fluorescence excitation spectra of a supersonic expansion of B atoms entrained in Ar at high source backing pressures display several features not assignable to the BAr complex. Resonance fluorescence is not observed, but instead emission from the lower 3s state. Size-selected fluorescence depletion spectra show that these features in the excitation spectrum are primarily due to the BAr2 complex. This electronic transition within BAr2 is modeled theoretically, similarly to our earlier study of the 3s <-- 2p transition [M. H. Alexander , J. Chem. Phys. 106, 6320 (1997)]. The excited potential energy surfaces of the fivefold degenerate B(2s2p(2) D-2) state within the ternary complex are computed in a pairwise-additive model employing diatomic BAr potential energy curves which reproduce our previous experimental observations on the electronic states emanating from the B(D-2)+Ar asymptote. The simulated absorption spectrum reproduces reasonably well the observed fluorescence depletion spectrum. The theoretical model lends insight into the energetics of the approach of B to multiple Ar atoms, and how the orientation of B p-orbitals governs the stability of the complex. (C) 2000 American Institute of Physics. [S0021-9606(00)01210-1].