Potassium halide adducts of the form K2X(+) (X = F, CI, Br, and I) desorbed from neutral salts by high power, pulsed, infrared laser radiation are detected in abundance by Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometry. FT-ICR detection of the K2X(+) adduct is favored at increased laser power densities (> 10(8) W/cm(2)) and at trapping potentials below 3 V, independent of X. In contrast, detection of K(+) is promoted at laser power densities below 10(8) W/cm(2) or at higher trapping potentials, with a threshold for trapping that is strongly dependent on X. When laser desorption/ionization (LDI)/FT-ICR is performed on 1:1 mixtures of KX and organic molecules, ejection pulses applied continuously at the cyclotron resonance frequency of K2X(+) inhibit formation of the cation-attached product, [M + K](+). Conversely, resonance ejection of K(+) enhances [M + K](+), apparently by reducing the matrix ion population trapped in the cell. In evaluating higher molecular weight adducts, only K3F 2 (+) formed in abundance by laser desorption of KF is found through double resonance experiments to contribute significantly to formation of [M + K](+). Finally, among the potassium halides, KI generates the highest ratio of detected K2X(+) to K(+) at low trapping potentials and is therefore best suited for cation-transfer reactions in infrared LDI/FT-ICR experiments performed at power densities in the 10(8) W/cm(2) range.