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Title: Ion imaging study of reaction dynamics in the N{sup +}+ CH{sub 4} system

Abstract

The velocity map ion imaging method is applied to the ion-molecule reactions of N{sup +} with CH{sub 4}. The velocity space images are collected at collision energies of 0.5 and 1.8 eV, providing both product kinetic energy and angular distributions for the reaction products CH{sub 4}{sup +}, CH{sub 3}{sup +}, and HCNH{sup +}. The charge transfer process is energy resonant and occurs by long-range electron transfer that results in minimal deflection of the products. The formation of the most abundant product, CH{sub 3}{sup +}, proceeds by dissociative charge transfer rather than hydride transfer, as reported in earlier publications. The formation of HCNH{sup +} by C-N bond formation appears to proceed by two different routes. The triplet state intermediates CH{sub 3}NH{sup +} and CH{sub 2}NH{sub 2}{sup +} that are formed as N{sup +}({sup 3}P) approaches CH{sub 4} may undergo sequential loss of two hydrogen atoms to form ground state HCNH{sup +} products on a spin-allowed pathway. However, the kinetic energy distributions for formation of HCNH{sup +} extend past the thermochemical limit to form HCNH{sup +}+ 2H, implying that HCNH{sup +} may also be formed in concert with molecular hydrogen, and requiring that intersystem crossing to the singlet manifold must occur inmore » a significant ({approx}25%) fraction of reactive collisions. We also report GAUSSIAN G2 calculations of the energies and structures of important singlet and triplet [CNH{sub 4}{sup +}] complexes that serve as precursors to product formation.« less

Authors:
;  [1]
  1. Department of Chemistry, University of Rochester, Rochester, New York 14627 (United States)
Publication Date:
OSTI Identifier:
22099064
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 137; Journal Issue: 15; Other Information: (c) 2012 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANGULAR DISTRIBUTION; CHARGE EXCHANGE; DISSOCIATION; ELECTRON TRANSFER; EV RANGE 01-10; GROUND STATES; HYDRIDES; HYDROGEN; ION-MOLECULE COLLISIONS; KINETIC ENERGY; METHANE; MOLECULAR STRUCTURE; REACTION KINETICS; TRIPLETS; VELOCITY

Citation Formats

Pei, Linsen, and Farrar, James M. Ion imaging study of reaction dynamics in the N{sup +}+ CH{sub 4} system. United States: N. p., 2012. Web. doi:10.1063/1.4759265.
Pei, Linsen, & Farrar, James M. Ion imaging study of reaction dynamics in the N{sup +}+ CH{sub 4} system. United States. doi:10.1063/1.4759265.
Pei, Linsen, and Farrar, James M. Sun . "Ion imaging study of reaction dynamics in the N{sup +}+ CH{sub 4} system". United States. doi:10.1063/1.4759265.
@article{osti_22099064,
title = {Ion imaging study of reaction dynamics in the N{sup +}+ CH{sub 4} system},
author = {Pei, Linsen and Farrar, James M.},
abstractNote = {The velocity map ion imaging method is applied to the ion-molecule reactions of N{sup +} with CH{sub 4}. The velocity space images are collected at collision energies of 0.5 and 1.8 eV, providing both product kinetic energy and angular distributions for the reaction products CH{sub 4}{sup +}, CH{sub 3}{sup +}, and HCNH{sup +}. The charge transfer process is energy resonant and occurs by long-range electron transfer that results in minimal deflection of the products. The formation of the most abundant product, CH{sub 3}{sup +}, proceeds by dissociative charge transfer rather than hydride transfer, as reported in earlier publications. The formation of HCNH{sup +} by C-N bond formation appears to proceed by two different routes. The triplet state intermediates CH{sub 3}NH{sup +} and CH{sub 2}NH{sub 2}{sup +} that are formed as N{sup +}({sup 3}P) approaches CH{sub 4} may undergo sequential loss of two hydrogen atoms to form ground state HCNH{sup +} products on a spin-allowed pathway. However, the kinetic energy distributions for formation of HCNH{sup +} extend past the thermochemical limit to form HCNH{sup +}+ 2H, implying that HCNH{sup +} may also be formed in concert with molecular hydrogen, and requiring that intersystem crossing to the singlet manifold must occur in a significant ({approx}25%) fraction of reactive collisions. We also report GAUSSIAN G2 calculations of the energies and structures of important singlet and triplet [CNH{sub 4}{sup +}] complexes that serve as precursors to product formation.},
doi = {10.1063/1.4759265},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 15,
volume = 137,
place = {United States},
year = {2012},
month = {10}
}