Dissociative Photoionization and Thermochemistry of Dihalomethane Compounds Studied by Threshold Photoelectron Photoion Coincidence Spectroscopy

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 109; no. 9; pp. 1802 - 1809
• Main Authors: Lago, A. F, Kercher, James P, Bödi, András, Sztáray, Bálint, Miller, B, Wurzelmann, D, Baer, Tomas
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 10-03-2005
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp045337s

The dissociative photoionization studies have been performed for a set of dihalomethane CH2XY (X,Y = Cl, Br, and I) molecules employing the threshold photoelectron photoion coincidence (TPEPICO) technique. Accurate dissociation onsets for the first and second dissociation limits have been recorded in the 10−13 eV energy range, and ionization potentials have been measured for these compounds. By using our experimental dissociation onsets and the known heat of formation of CH2Cl2 molecule, it has been possible to derive the 0 and 298 K heats of formation of all six neutral dihalomethanes as well as their ionic fragments, CH2Cl+, CH2Br+, and CH2I+, to a precision better than 3 kJ/mol. These new measurements serve to fill the lack of reliable experimental thermochemical information on these molecules, correct the old literature values by up to 19 kJ/mol, and reduce their uncertainties. From our thermochemical results it has also been possible to derive a consistent set of bond dissociation energies for the dihalomethanes.