Infrared multiphoton dissociation of unsubstituted metal carbonyls at 5 μm

Mei-Kuen Au, P. A. Hackett, M. Humphries, P. John

Research output: Contribution to journalArticle

Abstract

A frequency-doubled carbon dioxide laser of modest output energy (1 mJ) has been used to study, for the first time, the infrared multiphoton absorption by, and dissociation of, the unsubstituted carbonyls of vanadium, chromium, iron, nickel, molybdenum, and tungsten. The multiphoton absorption cross-sections measured for Ni(CO)4, Fe(CO)5, Cr(CO)6, Mo(CO)6, and V(CO)6 are high (σ∼2×10-17) and ensure facile multiphoton dissociation. In focussed beams a pressure independent reaction yield proportional to the 1.5 power of the beam energy is observed for Fe(CO)5, Cr(CO)6, and Mo(CO)6 implying threshold fluences of only 32, 25, and 26 mJ cm-2, respectively. The stoichiometry of the reaction, observed by a pressure measurement technique, is consistent with production of metal atoms and carbon monoxide as final products for Ni(CO)4, Fe(CO)5, Cr(CO)6, and Mo(CO)6. This extensive decarbonylation along the ground state surface is consistent with recent studies of the photochemistry of these molecules from excited electronic states.

Original languageEnglish
Pages (from-to)43-49
Number of pages7
JournalApplied Physics B Photophysics and Laser Chemistry
Volume33
Issue number1
DOIs
Publication statusPublished - Jan 1984

Keywords

  • 82.50

ASJC Scopus subject areas

  • Engineering(all)

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