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.; Xie, C.; Guo, H.; Ushakov, V. G.; Troe, J.

doi:10.1016/j.ijms.2018.10.011

Item

ITEM ACTIONSEXPORT

Add to Basket

Local TagsRelease HistoryDetailsSummary

Released

Journal Article

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

MPS-Authors

/persons/resource/persons15934

Troe, J.
Emeritus Group of Spectroscopy and Photochemical Kinetics, MPI for Biophysical Chemistry, Max Planck Society;

External Resource

No external resources are shared

Fulltext (restricted access)

There are currently no full texts shared for your IP range.

Fulltext (public)

There are no public fulltexts stored in PuRe

Supplementary Material (public)

There is no public supplementary material available

Citation

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.

Cite as: https://hdl.handle.net/21.11116/0000-0002-BD4E-3

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.