Photodissociation Spectroscopy and Photofragment Imaging to Probe Fe+(Benzene)1,2 Dissociation Energies

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2023-03, Vol.127 (12), p.2795-2804
• Main Authors: Colley, Jason E., Dynak, Nathan J., Blais, John R. C., Duncan, Michael A.
• Format: Article
• Language: English
• Subjects: A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/acs.jpca.3c00735

Tunable laser photodissociation spectroscopy measurements and photofragment imaging experiments are employed to investigate the dissociation energy of the Fe+(benzene) ion–molecule complex. Additional spectroscopy measurements determine the dissociation energy of Fe+(benzene)2. The dissociation energies for Fe+(benzene) determined from the threshold for the appearance of the Fe+ fragment (48.4 ± 0.2 kcal/mol) and photofragment imaging (≤49.3 ± 3.2 kcal/mol) agree nicely with each other and with the value determined previously by collision-induced dissociation (49.5 ± 2.9 kcal/mol), but they are lower than the values produced by computational chemistry at the density functional theory level using different functionals recommended for transition-metal chemistry. The threshold measurement for Fe+(benzene)2 (43.0 ± 0.2 kcal/mol) likewise agrees with the value (44.7 ± 3.8 kcal/mol) from previous collision-induced dissociation measurements.