The 3s <-- 2p transition in the bNE(2) complex was observed in laser fluorescence excitation spectra of a supersonic expansion of B atoms entrained in Ne at high source backing pressures from a cooled beam source. A variational Monte-Carlo treatment of the ground vibrational state of the BNe2 complex was carried out, using B(2p, 3s)Ne potential energy curves validated by comparison of computed and experimental spectra of the BNe complex. A subsequent simulation of the 3s <-- 2p transition reproduces nearly quantitatively the experimental spectrum. (C) 2004 Elsevier B.V. All rights reserved.