Simplified Multiple-Well Approach for the Master Equation Modeling of Blackbody Infrared Radiative Dissociation of Hydrated Carbonate Radical Anions
Magdalena Salzburger, Milan Ončák, Christian van der Linde, Martin K. Beyer
Abstract
at 250-330 K to determine water binding energies and assess the influence of multiple isomers on the dissociation kinetics. The ions are trapped in a Fourier-transform ion cyclotron resonance mass spectrometer, mass selected, and their BIRD kinetics are recorded at varying temperatures. Experimental BIRD rates as a function of temperature are fitted with rates obtained from master equation modeling (MEM), using the water binding energy as a fit parameter. MEM accounts for the absorption and emission of photons from black-body radiation, described with harmonic frequencies and infrared intensities from quantum chemical calculations. The dissociation rates as a function of internal energy are calculated by Rice-Ramsperger-Kassel-Marcus theory. Both single-well and multiple-well MEM approaches are used. Dissociation energies derived in this way from the experimental data are 56 ± 6 and 45 ± 3 kJ/mol for the first and second water molecules, respectively. They agree within error limits with the ones predicted by ab initio calculations done at the CCSD(T)/aug-cc-pVQZ//CCSD/aug-cc-pVDZ level of theory. We show that the multiple-well MEM approach described here yields superior results in systems with several low-lying minima, which is the typical situation for hydrated ions.