Experimental and Theoretical Studies of Co(CH_4)_x^+ with x = 1-4
Abstract
The sequential bond energies of Co(CH_4)_x^+, x = 1-4, are determined experimentally and theoretically. Collision-induced dissociation studies conducted using a guided ion beam tandem mass spectrometer yield 0 K bond energies of D_o[Co^+-Xe] = 0.85 ± 0.07 eV, D_o[Co^+-CH_4] = 0.93 ± 0.06 eV, D_o[Co(CH_4)^+-CH_4] = 1.00 ± 0.05 eV, D_0[Co(CH_4)_2^+-CH_4] = 0.41 ± 0.05 eV, and D_o[Co(CH-4)_3^+-CH_4] = 0.67 ± 0.06 eV. These numbers are in excellent agreement with ab initio calculations which lead to values of D_e[Co^+-(CH_4)] = 0.93 eV, D_e[Co(CH_4)^+-CH_4] = 1.00 eV, D_e[Co(CH_4)_2+-CH_4] ≈ 0.40 eV, and D_e[Co(CH_4)_3^+-CH_4] ≈ 0.70 eV. We find that the nonmonotonic behavior in the sequential binding energies arises from changes in hybridization at the metal center as the third ligand is bound.
Additional Information
© 1995 American Chemical Society. Received: November 7, 1994; In Final Form: February 20, 1995. J.K.P. was supported in part by a fellowship from BP America. This research is supported in part by the National Science Foundation, CHE-9221241 (P.B.A.) and CHE-9100284 (W.A.G.). Facilities of the Materials and Molecular Simulation Center were supported by grants from DOE/AICD, Allied-Signal, BP America, Asahi Chemical, Asahi Glass, Chevron Petroleum Technology Co., BF Goodrich, Teijin Ltd., Vestar, and Hughes Research Laboratories.Additional details
- Alternative title
- Experimental and Theoretical Studies of Co(CH4)x+ with x = 1-4
- Eprint ID
- 86626
- Resolver ID
- CaltechAUTHORS:20180525-113849310
- BP America
- CHE-9221241
- NSF
- CHE-9100284
- NSF
- Department of Energy (DOE)
- Allied-Signal
- Asahi Chemical
- Asahi Glass
- Chevron Petroleum Technology Co.
- BF Goodrich
- Teijin Ltd.
- Vestar
- Hughes Research Laboratories
- Created
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2018-05-25Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field