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Thermochemistry and energy partitioning in the charge separation reactions of doubly charged triatomic ions

J. Chem. Phys. 61, 1208 (1974); doi:10.1063/1.1681995

Issue Date: 1 August 1974

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R. G. Cooks, D. T. Terwilliger, and J. H. Beynon
Department of Chemistry, Purdue University, West Lafayette, Indiana 47907
Ion kinetic energy and appearance potential measurements have been used to study the unimolecular charge separation reactions of the triatomic ions CO<sub>2</sub><sup>2+</sup>, COS2+, CS<sub>2</sub><sup>2+</sup>, N2O2+, NO<sub>2</sub><sup>2 + [center-dot]</sup>, and SO<sub>2</sub><sup>2+</sup>. The experimentally determined metastable peak shapes have been compared with calculated peak shapes including calculations that determine both the average kinetic energy release and the distribution about this average. The product ion states have been assigned from the thermochemical data, and in all the reactions total spin and angular momentum are found to be conserved. There is evidence that the metastable peaks are associated with maxima on single potential surfaces rather than with a slow predissociation. For CO<sub>2</sub><sup>++</sup> and COS++ almost all the available energy is partitioned into translational energy of product separation. ©1974 American Institute of Physics
History: Received 8 February 1974
Permalink: http://link.aip.org/link/?JCPSA6/61/1208/1
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0021-9606 (print)   1089-7690 (online)
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REFERENCES (14)
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  1. For an over-all treatment see R. G. Cooks, J. H. Beynon, R. M. Caprioli, and G. R. Lester, Metastable Ions (Elsevier, Amsterdam, 1973).
  2. J. H. Beynon, R. M. Caprioli, and J. W. Richardson, J. Am. Chem. Soc. 93, 1852 (1971).
  3. (a) J. H. Beynon, R. M. Caprioli, W. E. Baitinger, and J. W. Amy, Org. Mass Spectrum. 3, 455 (1970);
  4. (b) J. H. Beynon, R. M. Caprioli, and J. W. Amy, Org. Mass Spectrom. 5, 229 (1971);
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    and E. G. Jones, J. H. Beynon, and R. G. Cooks, J. Chem. Phys. 57, 3207 (1972).

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