Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 131, Issue 38, Pages 13590-+Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja905459y
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Funding
- National Science Foundation [CHE-0748501]
- University of Michigan
- Direct For Mathematical & Physical Scien [748501] Funding Source: National Science Foundation
- Division Of Chemistry [748501] Funding Source: National Science Foundation
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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.
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