We report quantum mechanics calculations (B3LYP flavor of density functional theory) to determine the chemical reaction mechanism underlying the hypergolic reaction of pure HNO3 with N,N,N',N'- tetramethylethylenediamine (TMEDA) and N,N,N',N'-tetramethylmethylenediamine (TMMDA).TMEDA andTMMDA are dimethyl amines linked by two CH2 groups or one CH2 group, respectively, but ignite very differently withHNO 3.We explain this dramatic difference in terms of the role that N lone-pair electrons play in activating adjacent chemical bonds. We identify two key atomistic level factors that affect the ignition delay: (1) The exothermicity for formation of the dinitrate salt fromTMEDA orTMMDA. With only a single CH2 group between basic amines, the diprotonation of TMMDA results in much stronger electrostatic repulsion, reducing the heat of dinitrate salt formation by 6.3 kcal/mol. (2) The reaction of NO2with TMEDA or TMMDA, which is the step that releases the heat and reactive species required to propagate the reaction. Two factors of TMEDA promote the kinetics by providing routes with low barriers to oxidize the C: (a) formation of a stable intermediate with a C-C double bond and (b) the lower bond energy for breaking the C-C single bond (by 18 kcal/mol comparing to alkane) between two amines. Both factors would decrease the ignition delay for TMEDA versus TMMDA. The same factors also explain the shorter ignition delay of 1,4-dimethylpiperazine (DMPipZ) versus 1,3,5-trimethylhexahydro-1,3,5-triazine (TMTZ). These results indicate that TMEDA and DMPipZ are excellent green replacements for hydrazines as the fuel in bipropellants.