The reaction dynamics of the thermal gas-phase decomposition of 2,3-diazabicyclo (2.2.1)hept-2-ene-exo, exo-5,6-d2 have been investigated using classical trajectory methods on a semiempirical potential-energy surface. The global potential is written as a superposition of different reaction channel potentials containing bond stretching, bending and torsional terms, connected by parametrized switching functions. Reaction channels for stepwise and concerted cleavage of the two C–N bonds of the reactant have both been considered in construction of the potential. The geometries of 2,3-diazabicyclo(2.2.1)hept-2-ene, the diazenyl biradical and of the transition state corresponding to breaking of the remaining C–N bond of diazenyl biradical have been determined at the second order Möller–Plesset perturbation theory (MP2/6-31G*) and at Hartree–Fock (HF/6-31G*) levels, respectively. The bond dissociation energies have been estimated using the available thermochemical data and previously reported results for bicyclo(2.1.0)pentane [J. Chem. Phys. 101, 3729 (1994)]. The equilibrium geometries predicted by the semiempirical potential for reactants and products, the barrier height for thermal nitrogen extrusion from 2,3-diazabicyclo(2.2.1)hept-2-ene and the fundamental vibrational frequencies are in good to excellent agreement with the measured or ab initio calculated values. Using a projection method of the instantaneous Cartesian velocities onto the normal mode vectors and classical trajectory calculations, the dissociation dynamics of 2,3-diazabicyclo(2.2.1)hept-2-ene-exo, exo-5,6-d2 are investigated at several excitation energies in the range 60–175 kcal/mol. The results show the following: (1) The thermal reaction takes place with a preference for inversion of configuration in the reaction products, the exo-labeled bicyclo(2.1.0) pentane being the major product. The exo/endo ratio of bicyclo(2.1.0) pentane isomers is found to vary between 1.8–2.2 for the energy range considered. (2) For random energization of the vibrational modes, the energy dependence of the rate coefficients can be described by a RRK expression. (3) The significant broadening and overlapping of the power spectral bands, together with the disappearance of characteristic features in the power spectra of the internal coordinates calculated at different energies, indicate high intramolecular vibrational redistribution rates and global statistical behavior. (4) The energy partitioning among products shows that the internal energy is preferentially distributed into the vibrational degrees of freedom in BCP, while N2 is formed with small amounts of rotational and vibrational energies. Overall, the distribution of energy among the product degrees of freedom follows statistical predictions in the internal energy range investigated. (5) Stepwise dissociation of the C–N bonds is the predominant mechanism which characterizes the N2 elimination from the parent molecule. (6) Although statistical theories of reaction rates, such as Rice–Ramsperger–Kassel–Marcus (RRKM) theory, are unable to predict the product exo/endo ratio, this is not a result of the breakdown of the statistical assumption inherent in these theories, but rather to the fact that statistical theory does not address mechanistic questions related to post transition-state events. Although the results show that there is a near microcanonical distribution of energy in the 1,3-cyclopentanediyl radical, the system does not have sufficient time to explore all of the energetically accessible configuration space prior to the closure of the 1–3 bridgehead bond. The result is a nonstatistical exo/endo product ratio that deviates from the statistically expected result of unity.