Dependence of the branching ratio of C4H3+/C4H4+ on the parent ion energy in 2,4-hexadiyne ionic dissociation. Statistical theory and experiment

E. L. Chronister; D. M. Szaflarski; M. A. El-Sayed; J. Silberstein; I. Salman; R. D. Levine

doi:10.1021/j100321a026

Dependence of the branching ratio of C₄H₃⁺/C₄H₄⁺ on the parent ion energy in 2,4-hexadiyne ionic dissociation. Statistical theory and experiment

E. L. Chronister, D. M. Szaflarski, M. A. El-Sayed^*, J. Silberstein, I. Salman, R. D. Levine

^*Corresponding author for this work

Institute of Chemistry

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Abstract

The C₄H₃⁺/C₄H₄⁺ ratio of ions produced from the ionic dissociation of 2,4-hexadiyne as a result of the absorption of one vacuum UV photon or three UV laser photons is plotted as a function of the parent ion internal energy. The branching ratios were examined for parent ion internal energies in the range from 5 to 7 eV. These results are compared with statistical maximum entropy calculations. While the agreement between theory and experiment is not perfect, the best fit is found if one assumes that C₄H₃⁺ is produced from two dissociation channels (C₄H₃⁺ + C₂H₃ and C₄H₃⁺ + C₂H₂ + H) and that C₄H₄⁺ requires an activation entropy of -6.0 eu for its formation. Possible reasons are given for the disagreement between the observed and calculated behavior.

Original language	English
Pages (from-to)	2824-2827
Number of pages	4
Journal	Journal of Physical Chemistry
Volume	92
Issue number	10
DOIs	https://doi.org/10.1021/j100321a026
State	Published - 1988

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title = "Dependence of the branching ratio of C4H3+/C4H4+ on the parent ion energy in 2,4-hexadiyne ionic dissociation. Statistical theory and experiment",

abstract = "The C4H3+/C4H4+ ratio of ions produced from the ionic dissociation of 2,4-hexadiyne as a result of the absorption of one vacuum UV photon or three UV laser photons is plotted as a function of the parent ion internal energy. The branching ratios were examined for parent ion internal energies in the range from 5 to 7 eV. These results are compared with statistical maximum entropy calculations. While the agreement between theory and experiment is not perfect, the best fit is found if one assumes that C4H3+ is produced from two dissociation channels (C4H3+ + C2H3 and C4H3+ + C2H2 + H) and that C4H4+ requires an activation entropy of -6.0 eu for its formation. Possible reasons are given for the disagreement between the observed and calculated behavior.",

author = "Chronister, \{E. L.\} and Szaflarski, \{D. M.\} and El-Sayed, \{M. A.\} and J. Silberstein and I. Salman and Levine, \{R. D.\}",

year = "1988",

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T1 - Dependence of the branching ratio of C4H3+/C4H4+ on the parent ion energy in 2,4-hexadiyne ionic dissociation. Statistical theory and experiment

AU - Chronister, E. L.

AU - Szaflarski, D. M.

AU - El-Sayed, M. A.

AU - Silberstein, J.

AU - Salman, I.

AU - Levine, R. D.

PY - 1988

Y1 - 1988

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AB - The C4H3+/C4H4+ ratio of ions produced from the ionic dissociation of 2,4-hexadiyne as a result of the absorption of one vacuum UV photon or three UV laser photons is plotted as a function of the parent ion internal energy. The branching ratios were examined for parent ion internal energies in the range from 5 to 7 eV. These results are compared with statistical maximum entropy calculations. While the agreement between theory and experiment is not perfect, the best fit is found if one assumes that C4H3+ is produced from two dissociation channels (C4H3+ + C2H3 and C4H3+ + C2H2 + H) and that C4H4+ requires an activation entropy of -6.0 eu for its formation. Possible reasons are given for the disagreement between the observed and calculated behavior.

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Dependence of the branching ratio of C₄H₃⁺/C₄H₄⁺ on the parent ion energy in 2,4-hexadiyne ionic dissociation. Statistical theory and experiment

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