What do matrix-assisted laser desorption/ionization mass spectra reveal about ionization mechanisms?

We present ion mass spectra obtained by matrix-assisted laser desorption/ionization for analytes of approximately 1000 Da across the largest range of wavelengths and pulse durations to date. The matrix used in all cases was 2,5-dihydroxybenzoic acid. Based on the data and fundamentals of laser-material interactions, we evaluated the plausibility of discriminating among such ion formation mechanisms as multiphoton ionization and excited-state ionization from mass spectra alone. Some previously proposed mechanisms appear unlikely for the matrix-analyte systems that we studied, casting doubt on their general applicability. Moreover, although analysis of mass spectra can apparently exclude certain mechanisms, it cannot establish which of several competing mechanisms is actually operative. This is particularly true with respect to variations in pulse duration and wavelength.