期刊
JOURNAL OF CHEMICAL PHYSICS
卷 154, 期 13, 页码 -出版社
AMER INST PHYSICS
DOI: 10.1063/5.0041074
关键词
-
资金
- Division of Chemical Sciences, Geosciences and Biosciences, Office of Basic Energy Sciences (BES), U.S. Department of Energy (USDOE)
- U.S. Department of Energy's National Nuclear Security Administration [DE-NA-0003525]
It is found that ultraviolet photoexcitation of iron pentacarbonyl leads to the formation of different iron carbonyl compounds through various photodissociation pathways, including iron tricarbonyl, iron tetracarbonyl, and iron dicarbonyl.
It is well known that ultraviolet photoexcitation of iron pentacarbonyl results in rapid loss of carbonyl ligands leading to the formation of coordinatively unsaturated iron carbonyl compounds. We employ ultrafast mid-infrared transient absorption spectroscopy to probe the photodissociation dynamics of gas-phase iron pentacarbonyl following ultraviolet excitation at 265 and 199 nm. After photoexcitation at 265 nm, our results show evidence for sequential dissociation of iron pentacarbonyl to form iron tricarbonyl via a short-lived iron tetracarbonyl intermediate. Photodissociation at 199 nm results in the prompt production of Fe(CO)(3) within 0.25 ps via several energetically accessible pathways. An additional 15 ps time constant extracted from the data is tentatively assigned to intersystem crossing to the triplet manifold of iron tricarbonyl or iron dicarbonyl. Mechanisms for formation of iron tetracarbonyl, iron tricarbonyl, and iron dicarbonyl are proposed and theoretically validated with one-dimensional cuts through the potential energy surface as well as bond dissociation energies. Ground state calculations are computed at the CCSD(T) level of theory and excited states are computed with EOM-EE-CCSD(dT).
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