An empirical approach to estimation of critical energies by using a quadrupole ion trap.

A simple energy-resolved mass spectrometric technique is described for the estimation of critical energies for dissociation of ions via threshold collisional activation measurements in a quadrupole ion trap. The method is calibrated by using compounds with well-defined dissociation energies, and separate calibration curves must be constructed for radical ions that are bound by covalent bonds versus hydrogen-bonded complexes. For these sets of experiments, the threshold point is defined as the activation voltage required for the fragment ion intensity to be 10% of the total ion intensity. A plot of threshold activation voltage of the calibrant versus literature critical energies shows a near-linear function, and accuracies are estimated as better than ± 6 kcal/mol. The q z value during activation seems to have little effect on the threshold voltages as long as very low q z values that cause ion ejection are avoided. Activation periods that are substantially longer than 10-ms result in nonlinear behavior in the calibration curves for ions that have critical energies above 30 kcal/mol. This energy-resolved method was also useful for the estimation of critical energies of complexes bound by electrostatic forces, such as hydrogen-bonding interactions. A quantitative evaluation of proton-bound polyether-amine complexes showed that the number of available hydrogen-binding sites, the gas-phase basicities of the polyether and amine components, and the ability of the complex to attain the most favorable near-linear hydrogen bonds correlate with the threshold values.