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  Mechanistic details of the MnO+ + H-2/D-2 reaction through temperature-dependent kinetics and statistical modeling.

Sweeny, B. C., Pan, H., Ard, S. G., Shuman, N. S., Viggiano, A. A., Keyes, N., et al. (2019). Mechanistic details of the MnO+ + H-2/D-2 reaction through temperature-dependent kinetics and statistical modeling. International Journal of Mass Spectrometry, 435, 26-33. doi:10.1016/j.ijms.2018.10.011.

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Item Permalink: http://hdl.handle.net/21.11116/0000-0002-BD4E-3 Version Permalink: http://hdl.handle.net/21.11116/0000-0003-B59C-1
Genre: Journal Article

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3017725.pdf (Publisher version), 2MB
 
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 Creators:
Sweeny, B. C., Author
Pan, H., Author
Ard, S. G., Author
Shuman, N. S., Author
Viggiano, A. A., Author
Keyes, N., Author
Xie, C., Author
Guo, H., Author
Ushakov, V. G., Author
Troe, J.1, Author              
Affiliations:
1Emeritus Group of Spectroscopy and Photochemical Kinetics, MPI for Biophysical Chemistry, Max Planck Society, ou_578625              

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Free keywords: H-2 activation; Metal catalysis; Statistical modelling; Temperature dependent kinetics
 Abstract: The temperature dependencies of the reactions MnO+ + H-2/D-2 from 150 to 600 K are measured in a selected- ion flow tube apparatus. The reactions are approximately 15% efficient at room temperature with rate constants (k = 2.7 +/- 0.7 x 10(-10) cm(3) s(-1) for H-2 and 1.5 +/- 0.4 x 10(-10) cm(3) s(-1) for D-2 at 300 K) that vary as T-1.1 +/- 0.2 and T-1.3 +/- 0.2, respectively. Both Mn+ and MnOH+/D+ products are observed, with Mn+ being the minority product in the H-2 reaction, but the majority product in the D-2 reaction. Reaction coordinates are explored using a variety of density functional methods, with quantitative but not qualitative differences in the results. Unlike the analogous FeO+ + H-2 reaction, no evidence for spin inversion prior to the rate-limiting transition state is found. A crossing between septet and quintet potential energy surfaces in the product well exists, and the possibility of spin inversion on the way to products is discussed. The reaction coordinates inform a statistical treatment of the reaction, which well reproduces all kinetic results, including the product branching inversion observed due to isotope substitution.

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Language(s): eng - English
 Dates: 2018-10-042019-01
 Publication Status: Published in print
 Pages: -
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 Rev. Method: Peer
 Identifiers: DOI: 10.1016/j.ijms.2018.10.011
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Title: International Journal of Mass Spectrometry
Source Genre: Journal
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Pages: - Volume / Issue: 435 Sequence Number: - Start / End Page: 26 - 33 Identifier: -