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Vibrational relaxation and isomerization of internally excited deuterated formyl and isoformyl cations has been investigated on the time scale of 2 ms to 12 s using the nearly interaction-free environment of an ion storage ring. De-excitation of the v 2 bending modes of DCO ϩ and DOC ϩ due to spontaneous radiative transitions was observed as a function of the storage time by measuring their foil-induced Coulomb explosion using three-dimensional coincident fragment imaging. No isomerization ofdoi:10.1063/1.1461812 fatcat:qi2gsabfhzcsviynckixp7ch3i