We present complete active space self-consistent field (CASSCF) ab initio molecular dynamics (AIMD) simulations of the preparation of the metastable species vinylidene, and its subsequent, highly exothermic isomerization to acetylene, via electron removal from vinylidene anion (D2C=C- --> D2C=C: --> DC=CD). After equilibrating vinylidene anion-d(2) at either 600 +/- 300 K (slightly below the isomerization barrier) or 1440 K +/- 720 K (just above the isomerization barrier), we remove an electron to form a vibrationally excited singlet vinylidene-d(2) and follow its dynamical evolution for 1.0 ps. Remarkably, we find that none of the vinylidenes equilibrated at 600 K and only 20% of the vinylidenes equilibrated at 1440 K isomerized, suggesting average lifetimes >1 ps for vibrationally excited vinylidene-d(2). Since the anion and neutral vinylidene are structurally similar, and yet extremely different geometrically from the isomerization transition state (TS), neutral vinylidene is not. formed near the TS so that it must Live until it has sufficient instantaneous kinetic energy in the correct vibrational models). The origin of the delay is explained via both orbital rearrangement and intramolecular vibrational energy redistribution (IVR) effects. Unique signatures of the isomerization dynamics are revealed in the anharmonic vibrational frequencies extracted from the AIMD, which should be observable by ultrafast vibrational spectroscopy and in fact are consistent with currently available experimental spectra. Most interestingly, of those trajectories that did isomerize, every one of them violated conventional transition-state theory by recrossing back to vinylidene multiple times, against conventional notions that expect highly exothermic reactions to be irreversible. The dynamical motion responsible for the multiple barrier recrossings involves strong mode-coupling between the vinylidene CD2 rock and a local acetylene DCC bend mode that has been recently observed experimentally. The multiple barrier recrossings can be used, via a generalized definition of lifetime, to reconcile extremely disparate experimental estimates of vinylidene's lifetime (differing by at least 6 orders of magnitude). Last, a caveat: These results are constrained by the approximations inherent in the simulation (classical nuclear motion, neglect of rotation-vibration coupling, and restriction to C-s symmetry); refinement of these predictions may be necessary when more exact simulations someday become feasible.