The addition of hydroxyl radical to benzene leading to the formation of the hydroxyl-2,4-cyclohexadienyl radical (benzene-OH adduct, BOH) initiates the atmospheric oxidation of benzene. This reaction and subsequent reactions of the BOH adduct with O-2 are chemically activated reactions. Rate constants of these chemically activated bimolecular reactions and unimolecular decompositions are analyzed using a quantum version of Rice-Ramsperger-Kassel theory (QRRK) for k(E) and a modified strong collision approach for falloff. Results of QRRK analyses show that stabilization channels of energized BOH and benzene-OH-O-2 (BOHO2) adducts are dominant in chemically activated reaction systems under atmospheric condition. Unimolecular reactions of stabilized adducts to products are also important. Thermodynamic parameters (Delta H(f)(degrees)298, S(degrees)298, and C-p(T)s) are calculated using group additivity techniques with evaluated bond energies (for Delta H(f)(degrees)298) and semiempirical PM3 molecular orbital calculations (for S(degrees)298 and C-p(T)s). A limited elementary reaction mechanism that includes 29 reactions and 26 species is developed with reverse reaction rates determined from species thermodynamic parameters and microscopic reversibility for each step. Simulation results of three reaction systems indicate that pseudo-equilibrium is attained and that equilibrium levels of the important BOH and BOHO2 adducts are controlled by thermodynamic properties. The most important bicyclic intermediate leading to ring cleavage products is adduct III. Rate constants of important bimolecular reactions are (k = A(T/K)(n) exp(-E(a)/RT), A in cm(3)/(mol s), E(a) in kcal/mol) : k(4), (4.65 x 10(15))(T/K)(-1.18) e(-1.23/RT) for C6H6 + OH double right arrow BOH; k(7), (3.55 x 10(36))(T/K)(-8.86) e(-3.79/RT) for BOH + O-2 double right arrow BOHO2; k(8), (1.73 x 10(10))(T/K)(-0.26) e(-8.28/RT) for BOH + O-2 double right arrow hexadienedial + OH; k(9), (7.06 x 10(14))(T/K)(-1.83) e-(5.36/RT) for BOH + O-2 double right arrow phenol + HO2; k(10), (2.14 x 10(15))(T/K)(-2.05) e(-4.69/RT) for BOH + O-2 double right arrow adduct III. Rate constants of important unimolecular reactions are (A in s(-1)) : kg, (2.04 x 10(25))(T/K)(-4.2) e(-24.5/RT) for BOH double right arrow 4 phenol + H; k(15), (6.30 x 10(40))(T/K)(-10.86) e(-19.4/RT) for BOHO2 double right arrow phenol + HO2; k(16), (1.43 x 10(42))(T/K)(-11.34) e(-18.8/RT) for BOHO2 double right arrow adduct III.