Energetics and kinetics of thermal ionization models of MALDI.

Thermal models of ultraviolet MALDI ionization based on the polar fluid concept are re-examined. Key components are very high solvating power of the fluidized matrix and consequent low reaction-free energy, attainment of thermal equilibrium in the fluid, and negligible recombination losses. None of these are found to hold in a MALDI event. The reaction-free energy in the hot matrix must be near the gas phase value, ion formation is too slow to approach equilibrium, and geminate recombination of autoprotolysis pairs greatly increases the initial loss rate. The maximum thermal ion yield is estimated to be many orders of magnitude below experimental values.