Photodissociation of hydrated hydrogen iodide clusters.
Using high-level ab initio calculations and excited state ab initio molecular dynamics simulations, we show that hydrated iodic acids release hydrogen radicals and/or hydrogen molecules as well as iodine radicals upon excitation. Its photoreaction process involving charge transfer to the solvent takes place in four steps: 1) hydration of the acid, 2) charge transfer to water upon excitation of hydrated acid, 3) detachment of the neutral iodine atom, and 4) detachment of the hydrogen radical. The iodine detachment process from excited hydrated hydro-iodic acids is exothermic and the detachment of hydrogen radicals from hydrated hydronium radicals is spontaneous if the initial kinetic energy of the cluster is high enough to get over the activation barrier of the detachment. The complete release of the radicals can be understood in terms of kinetics. This study shows how the hydrogen and halogen radicals are dissociated and released from their hydrated acids. Simple experiments corroborate our predicted mechanism for the release of hydrogen molecules from iodic acid in water by ultraviolet light.
Lee
Han Myoung
HM
Department of Chemistry, Center for Superfunctional Materials and Center for Basic Sciences, Pohang University of Science and Technology, San 31, Hyojadong, Namgu, Pohang, 790-784, Korea.
Kolaski
Maciej
M
Kim
Kwang S
KS
D000143:Acids / Q000737:chemistry* / Q000528:radiation effects; D003198:Computer Simulation; D005609:Free Radicals / Q000737:chemistry / Q000528:radiation effects; D006859:Hydrogen / Q000737:chemistry / Q000528:radiation effects; D007455:Iodine / Q000737:chemistry / Q000528:radiation effects; D017613:Iodine Compounds / Q000737:chemistry* / Q000528:radiation effects; D008956:Models, Chemical; D010777:Photochemistry; D011789:Quantum Theory; D014466:Ultraviolet Rays; D014867:Water / Q000737:chemistry
D000143:Acids; D005609:Free Radicals; D017613:Iodine Compounds; D014867:Water; C010466:hydroiodic acid; D006859:Hydrogen; D007455:Iodine