期刊
ACS EARTH AND SPACE CHEMISTRY
卷 1, 期 5, 页码 270-276出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsearthspacechem.7b00026
关键词
photochemistry; metal cycling ultrafast spectroscopy; mid-infrared vibrational spectroscopy; carbon dioxide radical anion
资金
- National Science Foundation [GG-1324791]
- Chemical Sciences, Geosciences, and Biosciences Division of the United States Department of Energy (U.S. DOE) [DE-AC02-05CH11231]
- Office of Basic Energy Sciences, Office of Science, U.S. DOE [DE-AC02-06CH11357]
- Directorate For Geosciences [1324791] Funding Source: National Science Foundation
- Division Of Earth Sciences [1324791] Funding Source: National Science Foundation
Iron(III) oxalate, Fe3+(C2O4)(3)(3-), is a photoactive metal organic complex found in natural systems and used to quantify photon flux as a result of its high absorbance and reaction quantum yield. It also serves as a model complex to understand metal carboxylate complex photolysis because the mechanism of photolysis and eventual production of CO2 is not well understood for any system. We employed pump/probe mid-infrared transient absorption spectroscopy to study the photolysis reaction of the iron(III) oxalate ion in D2O and H2O up to 3 ns following photoexcitation. We find that intramolecular electron transfer from oxalate to iron occurs on a sub-picosecond time scale, creating iron(II) complexed by one oxidized and two spectator oxalate ligands. Within 40 ps following electron transfer, the oxidized oxalate molecule dissociates to form free solvated CO2(aq) and a species inferred to be CO2 center dot- based on the appearance of a new vibrational absorption band and ab initio simulation. This work provides direct spectroscopic evidence for the first mechanistic steps in the photolysis reaction and presents a technique to analyze other environmentally relevant metal carboxylate photolysis reactions.
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