When infrared active molecular ions are stored in a heavy-ion storage ring,
a fast beam of vibrationally and rotationally relaxed molecules can be obt
ained. This opens up new opportunities for various experimental studies in
molecular ion physics, particularly those involved with spectroscopy and di
ssociation dynamics of excited states. The analysis of such experiments is
facilitated by the fact that the information on the initial states is able
to identify and, therefore, eliminate them from the assignment problem. Mor
eover, when the intensity of the measured transitions is monitored as a fun
ction of storage time, the dependence of these processes on the degree of i
nternal relaxation is revealed. We demonstrate these general principles by
application to near-threshold dissociation spectroscopy of the OH+ molecula
r ion. The structure of quasibound levels near the dissociation limit of OH
+ and its dissociation energy are deduced.