Gas-phase study of the group VI transition metal tricarbonyl complexes by negative-ion photoelectron spectroscopy (Poster Paper)

Ashfaq A. Bengali, Sean M. Casey, Chun Lin Cheng, Jonathan P. Dick, P. T. Fenn, Peter W Villalta, Doreen G Leopold

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Abstract

Photoelectron spectra are reported for Cr(CO)3-, Mo(CO)3- and W(CO)3- anions prepared from the corresponding metal hexacarbonyls in a flowing afterglow ion source. The 488.0 nm spectra were obtained at an electron kinetic energy resolution of 5 meV using a newly constructed apparatus. The spectra exhibit transitions between the ground electronic states of the anions and the neutral molecules, and they show weak activity in the symmetric CO stretching, MC stretching, MCO bending and CMC bending vibrational modes. The observed vibrational structure indicates that the anions, like the neutral molecules, have C3v equilibrium geometries. Force constants estimated for the neutral M(CO)3 molecules from the fundamental vibrational frequencies measured here are consistent with stronger metal-ligand bonding in the coordinatively unsaturated complexes than in the corresponding hexacarbonyls. Franck-Condon analyses of the spectra indicate only small differences between the equilibrium bond lengths and bond angles of the anions and the corresponding neutral molecules. The electron affinity pattern observed among the three group VI metal tricarbonyls is compared with characteristic trends within triads of transition metal atoms, and within the coinage metal dimer series. This comparison, combined with the results of previously reported theoretical calculations, suggests that the extra electron in the M(CO)3- anions occupies an sp hybrid orbital. Electron affinities of 1.349 eV, 1.337 eV, and 1.859 eV (all ± 0.006 eV) are obtained for Cr(CO)3, Mo(CO)3, and W(CO)3 respectively.

Original languageEnglish (US)
Title of host publicationProceedings of SPIE - The International Society for Optical Engineering
PublisherPubl by Int Soc for Optical Engineering
Pages106-117
Number of pages12
ISBN (Print)0819407844
StatePublished - Jan 1 1992
EventOptical Methods for Time- and State-Resolved Chemistry - Los Angeles, CA, USA
Duration: Jan 23 1992Jan 25 1992

Publication series

NameProceedings of SPIE - The International Society for Optical Engineering
Volume1638
ISSN (Print)0277-786X

Other

OtherOptical Methods for Time- and State-Resolved Chemistry
CityLos Angeles, CA, USA
Period1/23/921/25/92

Fingerprint

Carbon Monoxide
Photoelectron spectroscopy
Metal complexes
negative ions
Transition metals
Spectroscopy
Negative ions
Metals
Gases
transition metals
photoelectron spectroscopy
vapor phases
anions
Molecules
Electron
Electron affinity
Anions
Bending (deformation)
electron affinity
metals

Cite this

Bengali, A. A., Casey, S. M., Cheng, C. L., Dick, J. P., Fenn, P. T., Villalta, P. W., & Leopold, D. G. (1992). Gas-phase study of the group VI transition metal tricarbonyl complexes by negative-ion photoelectron spectroscopy (Poster Paper). In Proceedings of SPIE - The International Society for Optical Engineering (pp. 106-117). (Proceedings of SPIE - The International Society for Optical Engineering; Vol. 1638). Publ by Int Soc for Optical Engineering.

Gas-phase study of the group VI transition metal tricarbonyl complexes by negative-ion photoelectron spectroscopy (Poster Paper). / Bengali, Ashfaq A.; Casey, Sean M.; Cheng, Chun Lin; Dick, Jonathan P.; Fenn, P. T.; Villalta, Peter W; Leopold, Doreen G.

Proceedings of SPIE - The International Society for Optical Engineering. Publ by Int Soc for Optical Engineering, 1992. p. 106-117 (Proceedings of SPIE - The International Society for Optical Engineering; Vol. 1638).

Research output: Chapter in Book/Report/Conference proceedingConference contribution

Bengali, AA, Casey, SM, Cheng, CL, Dick, JP, Fenn, PT, Villalta, PW & Leopold, DG 1992, Gas-phase study of the group VI transition metal tricarbonyl complexes by negative-ion photoelectron spectroscopy (Poster Paper). in Proceedings of SPIE - The International Society for Optical Engineering. Proceedings of SPIE - The International Society for Optical Engineering, vol. 1638, Publ by Int Soc for Optical Engineering, pp. 106-117, Optical Methods for Time- and State-Resolved Chemistry, Los Angeles, CA, USA, 1/23/92.
Bengali AA, Casey SM, Cheng CL, Dick JP, Fenn PT, Villalta PW et al. Gas-phase study of the group VI transition metal tricarbonyl complexes by negative-ion photoelectron spectroscopy (Poster Paper). In Proceedings of SPIE - The International Society for Optical Engineering. Publ by Int Soc for Optical Engineering. 1992. p. 106-117. (Proceedings of SPIE - The International Society for Optical Engineering).
Bengali, Ashfaq A. ; Casey, Sean M. ; Cheng, Chun Lin ; Dick, Jonathan P. ; Fenn, P. T. ; Villalta, Peter W ; Leopold, Doreen G. / Gas-phase study of the group VI transition metal tricarbonyl complexes by negative-ion photoelectron spectroscopy (Poster Paper). Proceedings of SPIE - The International Society for Optical Engineering. Publ by Int Soc for Optical Engineering, 1992. pp. 106-117 (Proceedings of SPIE - The International Society for Optical Engineering).
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abstract = "Photoelectron spectra are reported for Cr(CO)3-, Mo(CO)3- and W(CO)3- anions prepared from the corresponding metal hexacarbonyls in a flowing afterglow ion source. The 488.0 nm spectra were obtained at an electron kinetic energy resolution of 5 meV using a newly constructed apparatus. The spectra exhibit transitions between the ground electronic states of the anions and the neutral molecules, and they show weak activity in the symmetric CO stretching, MC stretching, MCO bending and CMC bending vibrational modes. The observed vibrational structure indicates that the anions, like the neutral molecules, have C3v equilibrium geometries. Force constants estimated for the neutral M(CO)3 molecules from the fundamental vibrational frequencies measured here are consistent with stronger metal-ligand bonding in the coordinatively unsaturated complexes than in the corresponding hexacarbonyls. Franck-Condon analyses of the spectra indicate only small differences between the equilibrium bond lengths and bond angles of the anions and the corresponding neutral molecules. The electron affinity pattern observed among the three group VI metal tricarbonyls is compared with characteristic trends within triads of transition metal atoms, and within the coinage metal dimer series. This comparison, combined with the results of previously reported theoretical calculations, suggests that the extra electron in the M(CO)3- anions occupies an sp hybrid orbital. Electron affinities of 1.349 eV, 1.337 eV, and 1.859 eV (all ± 0.006 eV) are obtained for Cr(CO)3, Mo(CO)3, and W(CO)3 respectively.",
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