1994
DOI: 10.1002/mas.1280130304
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Whither the statistical theory of mass spectra?

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Cited by 60 publications
(29 citation statements)
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“…Thus, just as in the case of thermal reactions, energy randomization is greatly facilitated by the fact that the initial conditions are already scattered all over phase space. 11,71,72 Since, in addition, the efficiency of anharmonic coupling increases with E, a nearly uniform distribution of trajectories in phase space can be achieved at high internal energies, even if the lifetime is very short.…”
Section: B Mechanism Of Phase Space Samplingmentioning
confidence: 99%
See 1 more Smart Citation
“…Thus, just as in the case of thermal reactions, energy randomization is greatly facilitated by the fact that the initial conditions are already scattered all over phase space. 11,71,72 Since, in addition, the efficiency of anharmonic coupling increases with E, a nearly uniform distribution of trajectories in phase space can be achieved at high internal energies, even if the lifetime is very short.…”
Section: B Mechanism Of Phase Space Samplingmentioning
confidence: 99%
“…The distributions of kinetic energy released during the fragmentation process ͑KERDs͒ contain information about the reaction dynamics [1][2][3][4][5][6][7][8][9][10] and provide a complementary and more severe test for the validity of the statistical theories of mass spectra than the measurement of the unimolecular reaction rate constants. 11 The maximum entropy method [12][13][14][15] has seldom been used for the analysis of the KERD data of ionic systems, mainly in the form of a surprisal analysis. 5,[16][17][18][19][20][21][22] Only recently have detailed maximum entropy analyses of KERDs of ionic systems been reported.…”
Section: Introductionmentioning
confidence: 99%
“…The usual picture is based on the RRKM [22][23][24][25][26] (Rice-Rampsberger-Kassel-Marcus) statistical theory of unimolecular dissociation. The expression of the rate constant k(E) depends on an enthalpic term (the critical energy E 0 ), and on the activation entropy (through a degeneracy factor and the density of states of the reactant and the transition state).…”
mentioning
confidence: 99%
“…Lorquet suggested that the future research into the ergodic nature of chemical reactions should be directed to the analysis of kinetic energy release distributions. 45 The results of the present study provide another merit of such an analysis. Namely, valuable fundamental information such as the symmetry of the reaction path and the tunneling through the barrier may also be obtained from the kinetic energy release data.…”
Section: Discussionmentioning
confidence: 70%