Theoretical study on the mechanism and kinetics of atmospheric reactions NH2OH + OOH and NH2CH3 + OOH
Mechanism and kinetics of NH 2 OH + OOH and NH 2 CH 3 + OOH reactions were studied at the B3LYP and M062X levels of theory using the 6-311++G(3df, 3pd) basis set. The NH 2 OH + OOH and NH 2 CH 3 + OOH reactions proceed through different paths which lead to different products. Transition state structure and activation energy of each path were calculated. The calculated activation energies of hydrogen abstraction reactions were smaller than 25 kcal/mol and of substitution reactions are in the range of 50–70 kcal/mol. The rate constants were calculated using transition state theory (TST) modified for tunneling effect at 273–2000 K. • Mechanism of NH 2 OH and NH 2 CH 3 formation was investigated. • Mechanism and kinetics of NH 2 OH + OOH and NH 2 CH 3 + OOH reactions were studied. • Rate constants for these atmospheric reactions were calculated. • The rate constants for hydrogen abstraction were more than those for replacement reactions. • The calculated activation energies by the B3LYP were smaller than those obtained by the M062X.