Photodissociation dynamics of Fe(CO)5: Excited state lifetimes and energy disposal

Robert L. Whetten; Ke Jian Fu; Edward R. Grant

doi:10.1063/1.445582

Photodissociation dynamics of Fe(CO)₅: Excited state lifetimes and energy disposal

Robert L. Whetten, Ke Jian Fu, Edward R. Grant

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72 Scopus citations

Abstract

By examining the competition between fragmentation and photoionization of selectively photoexcited Fe(CO)₅ in a pulsed jet, we have been able to estimate wavelength dependent upper limits for excited state lifetimes. These range from 0.6 to 1.0 ps over the region from 290 to 310 nm. The nascent CO produced by this dissociation and subsequent multiple fragmentation is detected with rovibronic specificity by two-photon resonant four-photon ionization. Results on dynamics and lifetimes favor a dissociation model involving an unbound lowest ligand field state densely mixed with higher-lying ligand-field and charge transfer states. We also report the observation of highly efficient ion-molecule fragmentation reactions of Fe(II) with cold Fe(CO)₅, in which fragmentation branching ratios depend critically on the Fe(II) states produced by preceding resonance-enhanced two-photon ionization of free Fe atoms.

Original language	English (US)
Pages (from-to)	4899-4911
Number of pages	13
Journal	The Journal of Chemical Physics
Volume	79
Issue number	10
DOIs	https://doi.org/10.1063/1.445582
State	Published - 1983
Externally published	Yes

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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title = "Photodissociation dynamics of Fe(CO)5: Excited state lifetimes and energy disposal",

abstract = "By examining the competition between fragmentation and photoionization of selectively photoexcited Fe(CO)5 in a pulsed jet, we have been able to estimate wavelength dependent upper limits for excited state lifetimes. These range from 0.6 to 1.0 ps over the region from 290 to 310 nm. The nascent CO produced by this dissociation and subsequent multiple fragmentation is detected with rovibronic specificity by two-photon resonant four-photon ionization. Results on dynamics and lifetimes favor a dissociation model involving an unbound lowest ligand field state densely mixed with higher-lying ligand-field and charge transfer states. We also report the observation of highly efficient ion-molecule fragmentation reactions of Fe(II) with cold Fe(CO)5, in which fragmentation branching ratios depend critically on the Fe(II) states produced by preceding resonance-enhanced two-photon ionization of free Fe atoms.",

author = "Whetten, {Robert L.} and Fu, {Ke Jian} and Grant, {Edward R.}",

year = "1983",

doi = "10.1063/1.445582",

language = "English (US)",

volume = "79",

pages = "4899--4911",

journal = "The Journal of Chemical Physics",

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T1 - Photodissociation dynamics of Fe(CO)5

T2 - Excited state lifetimes and energy disposal

AU - Whetten, Robert L.

AU - Fu, Ke Jian

AU - Grant, Edward R.

PY - 1983

Y1 - 1983

N2 - By examining the competition between fragmentation and photoionization of selectively photoexcited Fe(CO)5 in a pulsed jet, we have been able to estimate wavelength dependent upper limits for excited state lifetimes. These range from 0.6 to 1.0 ps over the region from 290 to 310 nm. The nascent CO produced by this dissociation and subsequent multiple fragmentation is detected with rovibronic specificity by two-photon resonant four-photon ionization. Results on dynamics and lifetimes favor a dissociation model involving an unbound lowest ligand field state densely mixed with higher-lying ligand-field and charge transfer states. We also report the observation of highly efficient ion-molecule fragmentation reactions of Fe(II) with cold Fe(CO)5, in which fragmentation branching ratios depend critically on the Fe(II) states produced by preceding resonance-enhanced two-photon ionization of free Fe atoms.

AB - By examining the competition between fragmentation and photoionization of selectively photoexcited Fe(CO)5 in a pulsed jet, we have been able to estimate wavelength dependent upper limits for excited state lifetimes. These range from 0.6 to 1.0 ps over the region from 290 to 310 nm. The nascent CO produced by this dissociation and subsequent multiple fragmentation is detected with rovibronic specificity by two-photon resonant four-photon ionization. Results on dynamics and lifetimes favor a dissociation model involving an unbound lowest ligand field state densely mixed with higher-lying ligand-field and charge transfer states. We also report the observation of highly efficient ion-molecule fragmentation reactions of Fe(II) with cold Fe(CO)5, in which fragmentation branching ratios depend critically on the Fe(II) states produced by preceding resonance-enhanced two-photon ionization of free Fe atoms.

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Photodissociation dynamics of Fe(CO)₅: Excited state lifetimes and energy disposal

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