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Title: Experimental and ab initio studies of the reactive processes in gas phase i-C{sub 3}H{sub 7}Br and i-C{sub 3}H{sub 7}OH collisions with potassium ions

Abstract

Collisions between potassium ions and neutral i-C{sub 3}H{sub 7}Br and i-C{sub 3}H{sub 7}OH, all in their electronic ground state, have been studied in the 0.10–10.00 eV center of mass (CM) collision energy range, using the radiofrequency-guided ion beam technique. In K{sup +} + i-C{sub 3}H{sub 7}Br collisions KHBr{sup +} formation was observed and quantified, while the analogous KH{sub 2}O{sup +} formation in K{sup +} + i-C{sub 3}H{sub 7}OH was hardly detected. Moreover, formation of the ion-molecule adducts and their decomposition leading to C{sub 3}H{sub 7}{sup +} and either KBr or KOH, respectively, have been observed. For all these processes, absolute cross-sections were measured as a function of the CM collision energy. Ab initio structure calculations at the MP2 level have given information about the potential energy surfaces (PESs) involved. In these, different stationary points have been characterized using the reaction coordinate method, their connectivity being ensured by using the intrinsic-reaction-coordinate method. From the measured excitation function for KHBr{sup +} formation the corresponding thermal rate constant at 303 K has been calculated. The topology of the calculated PESs allows an interpretation of the main features of the reaction dynamics of both systems, and in particular evidence the important role played bymore » the potential energy wells in controlling the reactivity for the different reaction channels.« less

Authors:
; ; ; ;  [1];  [2]
  1. Departament de Química Orgànica, Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, Martí i Franquès, 1, 08028 Barcelona (Spain)
  2. Dipartimento di Fisica, Università degli Studi di Trento, 38123 Povo-Trento (Italy)
Publication Date:
OSTI Identifier:
22310751
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 141; Journal Issue: 16; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COLLISIONS; DECOMPOSITION; EXCITATION FUNCTIONS; GROUND STATES; ION BEAMS; MOLECULES; POTASSIUM BROMIDES; POTASSIUM IONS; POTENTIAL ENERGY; REACTION KINETICS; REACTIVITY

Citation Formats

López, E., Lucas, J. M., Andrés, J. de, Albertí, M., Aguilar, A., E-mail: a.aguilar@ub.edu, Bofill, J. M., and Bassi, D. Experimental and ab initio studies of the reactive processes in gas phase i-C{sub 3}H{sub 7}Br and i-C{sub 3}H{sub 7}OH collisions with potassium ions. United States: N. p., 2014. Web. doi:10.1063/1.4898377.
López, E., Lucas, J. M., Andrés, J. de, Albertí, M., Aguilar, A., E-mail: a.aguilar@ub.edu, Bofill, J. M., & Bassi, D. Experimental and ab initio studies of the reactive processes in gas phase i-C{sub 3}H{sub 7}Br and i-C{sub 3}H{sub 7}OH collisions with potassium ions. United States. https://doi.org/10.1063/1.4898377
López, E., Lucas, J. M., Andrés, J. de, Albertí, M., Aguilar, A., E-mail: a.aguilar@ub.edu, Bofill, J. M., and Bassi, D. 2014. "Experimental and ab initio studies of the reactive processes in gas phase i-C{sub 3}H{sub 7}Br and i-C{sub 3}H{sub 7}OH collisions with potassium ions". United States. https://doi.org/10.1063/1.4898377.
@article{osti_22310751,
title = {Experimental and ab initio studies of the reactive processes in gas phase i-C{sub 3}H{sub 7}Br and i-C{sub 3}H{sub 7}OH collisions with potassium ions},
author = {López, E. and Lucas, J. M. and Andrés, J. de and Albertí, M. and Aguilar, A., E-mail: a.aguilar@ub.edu and Bofill, J. M. and Bassi, D.},
abstractNote = {Collisions between potassium ions and neutral i-C{sub 3}H{sub 7}Br and i-C{sub 3}H{sub 7}OH, all in their electronic ground state, have been studied in the 0.10–10.00 eV center of mass (CM) collision energy range, using the radiofrequency-guided ion beam technique. In K{sup +} + i-C{sub 3}H{sub 7}Br collisions KHBr{sup +} formation was observed and quantified, while the analogous KH{sub 2}O{sup +} formation in K{sup +} + i-C{sub 3}H{sub 7}OH was hardly detected. Moreover, formation of the ion-molecule adducts and their decomposition leading to C{sub 3}H{sub 7}{sup +} and either KBr or KOH, respectively, have been observed. For all these processes, absolute cross-sections were measured as a function of the CM collision energy. Ab initio structure calculations at the MP2 level have given information about the potential energy surfaces (PESs) involved. In these, different stationary points have been characterized using the reaction coordinate method, their connectivity being ensured by using the intrinsic-reaction-coordinate method. From the measured excitation function for KHBr{sup +} formation the corresponding thermal rate constant at 303 K has been calculated. The topology of the calculated PESs allows an interpretation of the main features of the reaction dynamics of both systems, and in particular evidence the important role played by the potential energy wells in controlling the reactivity for the different reaction channels.},
doi = {10.1063/1.4898377},
url = {https://www.osti.gov/biblio/22310751}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 16,
volume = 141,
place = {United States},
year = {Tue Oct 28 00:00:00 EDT 2014},
month = {Tue Oct 28 00:00:00 EDT 2014}
}