Experimental and Theoretical Gas-Phase Acidities, Bond Dissociation Energies, and Heats of Formation of HClO x , x = 1−4

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 114; no. 12; pp. 4086 - 4092
• Main Authors: Meyer, Matthew M, Kass, Steven R
• Format: Journal Article
• Language: English
• Published: American Chemical Society 01.04.2010
• Subjects: A: Dynamics, Clusters, Excited States
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp100888k

Gas-phase deprotonation enthalpies were measured for chloric and perchloric acids and found to be 313.2 ± 3.3 and 299.9 ± 5.7 kcal mol−1, respectively. These values were combined with the previously reported electron affinities of ClO3 and ClO4 to obtain BDE(H−OClO2) = 97.6 ± 4.0 kcal mol−1 and BDE(H−OClO3) = 107.4 ± 6.1 kcal mol−1. These energetic determinations represent the first measurements of these quantities or extensive revisions of the currently available values. B3LYP, M06, M06−2X, G3, and G3B3 computations also were carried out to provide acidities, electron affinities, bond dissociation energies, and heats of formation via atomization energies for ClO x and HClO x , where x = 1−4. All of the methods do a reasonable job for the first three thermodynamic quantities but only M06 does a satisfactory job for the heats of formation, and its performance is similar to the highly accurate but extremely time intensive W4 method.