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Ionization transition states of the hydrogen molecular ion in external electric fields

S Kawai1, C Jaffé2 and T Uzer3

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The transition state is fundamental to modern theories of reaction dynamics. While transition state theory (TST) has been used mainly in chemical physics, it can be applied to any problem that involves some form of transformation, including half-scattering events such as ionization of Rydberg atoms. In this paper, we construct the ionization transition states of H+2 in an external electric field. In the process, we encounter and eliminate small divisors in our perturbation expansion and monitor its convergence using a new error criterion. The procedure is readily applicable to multiple Coulomb centres at large separations characteristic of Rydberg plasmas.


PACS

34.50.Gb Electronic excitation and ionization of molecules

34.50.-s Scattering of atoms and molecules

82.20.Db Transition state theory and statistical theories of rate constants

Subjects

Atomic and molecular physics

Chemical physics and physical chemistry

Dates

Issue 2 (28 January 2005)

Received 30 June 2004

Published 5 January 2005



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