H-Atom abstraction from CH(3)NHNH(2) by NO(2): CCSD(T)/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) and CCSD(T)/6-311+G(2df,p)//CCSD/6-31+G(d,p) calculations.
Stationary points of paths for H atom abstraction from CH(3)NHNH(2) (monomethylhydrazine) by NO(2) were characterized via CCSD(T)/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) and CCSD(T)/6-311+G(2df,p)//CCSD/6-31+G(d,p) calculations. Five transition states connecting CH(3)NHNH(2)-NO(2) complexes to a manifold that includes CH(3)NHNH-HONO, CH(3)NNH(2)-HONO, CH(3)NNH(2)-HNO(2), and CH(3)NHNH-HNO(2) complexes were identified. Transition states that connect CH(3)NHNH-HONO, CH(3)NNH(2)-HONO, CH(3)NNH(2)-HNO(2), and CH(3)NHNH-HNO(2) complexes to each other via H atom exchange and/or hindered internal rotation were also identified. The high point in the minimum energy path from the CH(3)NHNH(2) + NO(2) reactant asymptote to the manifold of HONO-containing product states is a transition state 8.6 kcal/mol above the reactant asymptote. From a kinetics standpoint, this value is considerably higher than the 5.9 kcal/mol value that was estimated for it based on theoretical results for H atom abstraction from NH(3) by NO(2).
McQuaid
Michael J
MJ
U.S. Army Research Laboratory, AMSRD-ARL-WM-BD, Aberdeen Proving Ground, Maryland 21005-5066, USA. mcquaid@arl.army.mil
Ishikawa
Yasuyuki
Y