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Spontaneous electron emission from hot silver dimer anions: Breakdown of the Born-Oppenheimer approximation

Journal article
Authors Emma K. Anderson
Alice F. Schmidt-May
P. K. Najeeb
Gustav Eklund
C. K. Chartkunchand
Steffan Rosen
Åsa Larson
Klavs Hansen
Henrik Cederquist
Henning Zettergren
Henning T. Schmidt
Published in Physical Review Letters
Volume 124
ISSN 0031-9007
Publication year 2020
Published at Department of Physics (GU)
Language en
Keywords Born-Oppenheimer approximation, storage ring, diatomic molecule
Subject categories Atom and Molecular Physics and Optics


We report the first experimental evidence of spontaneous electron emission from a homonuclear dimer anion through direct measurements of Ag−2 → Ag2 + e− decays on milliseconds and seconds timescales. This observation is very surprising as there is no avoided crossing between adiabatic energy curves to mediate such a process. The process is weak, yet dominates the decay signal after 100 ms when ensembles of internally hot Ag−2 ions are stored in the cryogenic ion-beam storage ring, DESIREE, for 10 s. The electron emission process is associated with an instantaneous, very large reduction of the vibrational energy of the dimer system. This represents a dramatic deviation from a Born-Oppenheimer description of dimer dynamics.

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