The spectroscopy and predissociation dynamics of CN-Ne were investigated using a variety of laser excitation techniques. Properties of the A (2) Pi state (vibrational levels upsilon = 2, 3, and 4) were characterized through studies of the A-X system. Both spin-orbit components of CN(A)-Ne were subject to predissociation. The upper component (Omega = 1/2) was predissociated by rapid spin-orbit relaxation (tau approximate to 6 ps, no vibrational dependence). The lower component (Omega = 3/2) was predissociated by the nonadiabatic internal conversion process, CN(A (2) Pi(3/2), upsilon)-Ne --> CN(X (2) Sigma(+), upsilon + 4) + Ne. Rates for predissociation by internal conversion were found to be exponentially dependent on the energy gap between the initial and final CN levels. These rates were relatively slow, permitting observation of rotationally resolved spectra for bands associated with the monomer Omega = 3/2 upsilon = 3 and 4 levels. Double resonance techniques were used to simplify the spectra and establish ro-vibronic assignments. Details of the intermolecular potential-energy surfaces were derived from these data. CN final state population distributions resulting from spin-orbit and internal conversion predissociation were characterized. For the former, excess energy was channeled into rotational excitation of CN, and levels of-parity were preferentially populated. The excess energy in predissociation by internal conversion was released primarily to translational recoil. In the accompanying paper, Yang and Alexander present ab initio potential surfaces for CN-Ne. From these surfaces they predict ro-vibronic energies and predissociation rates for levels associated with A, upsilon = 3. Results that depended on the A state surface alone were found to be in good agreement with experiment. Comparison of the internal conversion predissociation rates indicates that the ab initio calculations underestimated the coupling between the A and X states. (C) 1997 American Institute of Physics.