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  Spin-inversion and spin-selection in the reactions FeO+ + H-2 and Fe+ + N2O.

Ard, S. G., Johnson, R. S., Melko, J. J., Martinez, O., Shuman, N. S., Ushakov, V. G., et al. (2015). Spin-inversion and spin-selection in the reactions FeO+ + H-2 and Fe+ + N2O. Physical Chemistry Chemical Physics, 17(30), 19707-19717. doi:10.1039/c5cp01418b.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0028-31D0-F Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0028-31DE-4
Genre: Journal Article

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Ard, S. G., Author
Johnson, R. S., Author
Melko, J. J., Author
Martinez, O., Author
Shuman, N. S., Author
Ushakov, V. G., Author
Guo, H., Author
Troe, J.1, Author              
Viggiano, A. A., Author
Affiliations:
1Emeritus Group of Spectroscopy and Photochemical Kinetics, MPI for Biophysical Chemistry, Max Planck Society, ou_578625              

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 Abstract: The reactions of FeO+ with H-2 and of Fe+ with N2O were studied with respect to the production and reactivity of electronically excited Fe-4(+) cations. The reaction of electronic ground state (FeO+)-Fe-6 with H-2 was found to predominantly produce electronically excited Fe-4(+) as opposed to electronic ground state Fe-6(+) corresponding to a spin-allowed reaction. Fe-4(+) was observed to react with N2O with a rate constant of 2.3 (+0.3/-0.8) x 10(-11) cm(3) molecule(-1) s(-1), smaller than the ground state Fe-6(+) rate constant of 3.2 (+/- 0.5) x 10(-11) cm(3) molecule(-1) s(-1) (at room temperature). While the overall reaction of (FeO+)-Fe-6 with H-2 within the Two-State-Reactivity concept is governed by efficient sextet-quartet spin-inversion in the initial reaction complex, the observation of predominant Fe-4(+) production in the reaction is attributed to a much less efficient quartet-sextet back-inversion in the final reaction complex. Average spin-inversion probabilities are estimated by statistical modeling of spin-inversion processes and related to the properties of spin-orbit coupling along the reaction coordinate. The reaction of FeO+ with H-2 served as a source for Fe-4(+), subsequently reacting with N2O. The measured rate constant has allowed for a more detailed understanding of the ground state Fe-6(+) reaction with N2O, leading to a significantly improved statistical modeling of the previously measured temperature dependence of the reaction. In particular, evidence for the participation of electronically excited states of the reaction complex was found. Deexcitation of Fe-4(+) by He was found to be slow, with a rate constant <3 x 10(-14) cm(3) molecule(-1) s(-1).

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Language(s): eng - English
 Dates: 2015-06-252015
 Publication Status: Published in print
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 Rev. Method: Peer
 Identifiers: DOI: 10.1039/c5cp01418b
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Title: Physical Chemistry Chemical Physics
Source Genre: Journal
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Pages: - Volume / Issue: 17 (30) Sequence Number: - Start / End Page: 19707 - 19717 Identifier: -