Structurally selective geminate rebinding dynamics of solvent-caged radicals studied with nonequilibrium infrared echo spectroscopy.
Cyclopentadienylmolybdenum(II) tricarbonyl dimer exists in two different equilibrium conformations: trans and gauche. Ultrafast photoexcitation in the ultraviolet cleaves the Mo-Mo bond, permitting observation of the subsequent geminate rebinding reaction (t(rebinding) = 31.6 ps) by monitoring infrared bleach recoveries at frequencies corresponding to the CO stretches of the trans and gauche isomers, the time-resolved measurements revealed that the monomers rebind in the trans configuration only. Further insight into the rebinding reaction was obtained by mapping the full potential energy surface along the reaction coordinate using electronic-structure methods.
Baiz
Carlos R
CR
Department of Chemistry, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 40109, USA.
McCanne
Robert
R
Kubarych
Kevin J
KJ