A state-resolved recombination model is developed for direct simulation Monte Carlo method with a rovibrational database of collision cross-sections. The recombination is treated through a two-step binary interaction process, including orbiting-pair formation followed by subsequent stabilization involving a third body collision. The cross-section of the orbiting-pair formation and its lifetime are evaluated from the potential energy surface. This determines dissociation/recombination probabilities exclusively from cross-sections, rather than from equilibrium rate coefficients, thus making it more amenable to strong nonequilibrium flows modeled with DSMC. By calibrating the threshold scattering angle to-22.5 rad, the current model can reproduce the equilibrium recombination rate coefficients within the temperature range from T =3000K to 8000K. Good agreement between the current work and the previous model1 in the rovibrational heating and cooling relaxation processes is found.