Analysis of calculated NBO orbitals for the azide dataset reveals that most azides share a common natural Lewis structure (Figure ). The models for Tdec and log(IS) can both be readily understood and share analogous parameters. Both statistical models contain σ*(C-N3) occupancy descriptor; the coefficient for this descriptor is positive for Tdec and negative for log(IS). This parameter serves as a good readout for the inductive effects of substituents on the carbon of the azide group. Furthermore, both models contain a parameter that describes the NBO LUMO orbital of the N 2 ≡N 3 triple bond. The Tdec model indicates that azides with lower N 2 ≡N 3 NBO LUMO energies are more sensitive, and the log(IS) model suggests that compounds with a smaller N 2 ≡N 3 NBO HOMO/LUMO energy gap are more sensitive. These observations provide a consistent mechanistic picture of azide decomposition via extrusion of molecular nitrogen. Lastly, both models contain a parameter that describes the geometry/steric environment of the azide. In our model for Tdec, azides with a longer azide carbon-terminal nitrogen are predicted to have a lower Tdec. In our model for log(IS), azides with bulkier substituents are more sensitive.