Alkali chloride cluster ion dissociation examined by the kinetic method: Heterolytic bond dissociation energies, effective temperatures, and entropic effects

Lianming Wu, Jeff W. Denault, R. Graham Cooks, L. Drahos, K. Vékey

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20 Citations (Scopus)

Abstract

Branching ratios have been measured as a function of collision energy for the dissociation of mass-selected chloride-bound salt cluster ions, [Rb-35Cl-Mi]+, where Mi = Na, K, Cs. The extended version of the kinetic method was used to determine the heterolytic bond dissociation energy (HBDE) of Rb-Cl. The measured value of 480.8 ± 8.5 kJ/mol, obtained under single collision conditions, agrees with the HBDE value (482.0 ± 8.0 kJ/mol), calculated from a thermochemical cycle. The observed effective temperature of the collisionally activated salt clusters increases with laboratory-frame collision energy under both single- and multiple-collision conditions. Remarkably, the effective temperatures under multiple collision conditions are lower than those recorded under single-collision conditions at the same collision energy, a consequence of the inability of the triatomic ions to store significant amounts of internal energy. Laboratory-frame kinetic energy to internal energy transfer (T→V) efficiencies range from 3.8 to 13.5%. For a given cluster ion, the T→V efficiency decreases with increasing collision energy. Many features of the experimental results are accounted for using MassKinetics modeling (Drahos and Vékey, J. Mass Spectrom. 2001, 36, 237).

Original languageEnglish
Pages (from-to)1388-1395
Number of pages8
JournalJournal of the American Society for Mass Spectrometry
Volume13
Issue number12
DOIs
Publication statusPublished - Dec 2002

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Alkalies
Chlorides
Ions
Kinetics
Temperature
Salts
Energy Transfer
Kinetic energy
Energy transfer

ASJC Scopus subject areas

  • Structural Biology
  • Spectroscopy

Cite this

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title = "Alkali chloride cluster ion dissociation examined by the kinetic method: Heterolytic bond dissociation energies, effective temperatures, and entropic effects",
abstract = "Branching ratios have been measured as a function of collision energy for the dissociation of mass-selected chloride-bound salt cluster ions, [Rb-35Cl-Mi]+, where Mi = Na, K, Cs. The extended version of the kinetic method was used to determine the heterolytic bond dissociation energy (HBDE) of Rb-Cl. The measured value of 480.8 ± 8.5 kJ/mol, obtained under single collision conditions, agrees with the HBDE value (482.0 ± 8.0 kJ/mol), calculated from a thermochemical cycle. The observed effective temperature of the collisionally activated salt clusters increases with laboratory-frame collision energy under both single- and multiple-collision conditions. Remarkably, the effective temperatures under multiple collision conditions are lower than those recorded under single-collision conditions at the same collision energy, a consequence of the inability of the triatomic ions to store significant amounts of internal energy. Laboratory-frame kinetic energy to internal energy transfer (T→V) efficiencies range from 3.8 to 13.5{\%}. For a given cluster ion, the T→V efficiency decreases with increasing collision energy. Many features of the experimental results are accounted for using MassKinetics modeling (Drahos and V{\'e}key, J. Mass Spectrom. 2001, 36, 237).",
author = "Lianming Wu and Denault, {Jeff W.} and Cooks, {R. Graham} and L. Drahos and K. V{\'e}key",
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T1 - Alkali chloride cluster ion dissociation examined by the kinetic method

T2 - Heterolytic bond dissociation energies, effective temperatures, and entropic effects

AU - Wu, Lianming

AU - Denault, Jeff W.

AU - Cooks, R. Graham

AU - Drahos, L.

AU - Vékey, K.

PY - 2002/12

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N2 - Branching ratios have been measured as a function of collision energy for the dissociation of mass-selected chloride-bound salt cluster ions, [Rb-35Cl-Mi]+, where Mi = Na, K, Cs. The extended version of the kinetic method was used to determine the heterolytic bond dissociation energy (HBDE) of Rb-Cl. The measured value of 480.8 ± 8.5 kJ/mol, obtained under single collision conditions, agrees with the HBDE value (482.0 ± 8.0 kJ/mol), calculated from a thermochemical cycle. The observed effective temperature of the collisionally activated salt clusters increases with laboratory-frame collision energy under both single- and multiple-collision conditions. Remarkably, the effective temperatures under multiple collision conditions are lower than those recorded under single-collision conditions at the same collision energy, a consequence of the inability of the triatomic ions to store significant amounts of internal energy. Laboratory-frame kinetic energy to internal energy transfer (T→V) efficiencies range from 3.8 to 13.5%. For a given cluster ion, the T→V efficiency decreases with increasing collision energy. Many features of the experimental results are accounted for using MassKinetics modeling (Drahos and Vékey, J. Mass Spectrom. 2001, 36, 237).

AB - Branching ratios have been measured as a function of collision energy for the dissociation of mass-selected chloride-bound salt cluster ions, [Rb-35Cl-Mi]+, where Mi = Na, K, Cs. The extended version of the kinetic method was used to determine the heterolytic bond dissociation energy (HBDE) of Rb-Cl. The measured value of 480.8 ± 8.5 kJ/mol, obtained under single collision conditions, agrees with the HBDE value (482.0 ± 8.0 kJ/mol), calculated from a thermochemical cycle. The observed effective temperature of the collisionally activated salt clusters increases with laboratory-frame collision energy under both single- and multiple-collision conditions. Remarkably, the effective temperatures under multiple collision conditions are lower than those recorded under single-collision conditions at the same collision energy, a consequence of the inability of the triatomic ions to store significant amounts of internal energy. Laboratory-frame kinetic energy to internal energy transfer (T→V) efficiencies range from 3.8 to 13.5%. For a given cluster ion, the T→V efficiency decreases with increasing collision energy. Many features of the experimental results are accounted for using MassKinetics modeling (Drahos and Vékey, J. Mass Spectrom. 2001, 36, 237).

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