TY - JOUR
T1 - An ab initio molecular orbital study of potential energy surface of the NH 2 +NO 2 reaction
AU - Mebel, A. M.
AU - Hsu, C. C.
AU - Lin, Ming-Chang
AU - Morokuma, K.
PY - 1995/1/1
Y1 - 1995/1/1
N2 -
Potential energy surface of the reaction of NH
2
with NO
2
has been studied at the QCISD(T)/6-311G(d,p)//MP2/6-311G(d,p) +ZPC[MP2/6-311G(d,p)] and GAUSSIAN-2 (G2) levels of calculation. The reaction is shown to give three different groups of products. H
2
NO+NO can be produced by two different channels: (i) the barrierless association of the reactants to form H
2
NNO
2
1, followed by the nitro-nitrite rearrangement into H
2
NONO 3 and the ON bond scission and (ii) the association of H
2
N with ONO directly forming 3 without barrier, followed by the dissociation 3. The barrier for the nitro-nitrite rearrangement at the transition state (TS) 2, 31.2 kcal/mol with respect to 1, is 20.8 kcal/mol lower than the reactants at the best G2 level. The TS 2 is found to lie significantly lower and to have much tighter structure than those previously reported. The thermodynamically most stable N
2
O+H
2
O products can be formed from 1 by the complex mechanism (iii), involving 1,3-hydrogen shift from nitrogen to oxygen, rotation of the OH bond, H shift from one oxygen to another and migration of the second H atom from N to O leading to elimination of H
2
O. The rate-determining step is the 1,3-H shift at TS 4 which is 12.5 kcal/mol lower than NH
2
+NO
2
, but 8.3 kcal/mol higher than the barrier for the nitro-nitrite isomerization at TS 2 at the G2 level. N
2
+H
2
O
2
cannot be formed in the reaction, but several channels are shown to produce N
2
+2OH. All of them have as the rate-determining step the second 1,3-hydrogen shift from nitrogen to oxygen at TS 11 or 16, lying by 6.9 kcal/mol higher than NH
2
+NO
2
, and are not expected to compete with the reaction mechanisms producing H
2
NO+NO and N
2
O+H
2
O.
AB -
Potential energy surface of the reaction of NH
2
with NO
2
has been studied at the QCISD(T)/6-311G(d,p)//MP2/6-311G(d,p) +ZPC[MP2/6-311G(d,p)] and GAUSSIAN-2 (G2) levels of calculation. The reaction is shown to give three different groups of products. H
2
NO+NO can be produced by two different channels: (i) the barrierless association of the reactants to form H
2
NNO
2
1, followed by the nitro-nitrite rearrangement into H
2
NONO 3 and the ON bond scission and (ii) the association of H
2
N with ONO directly forming 3 without barrier, followed by the dissociation 3. The barrier for the nitro-nitrite rearrangement at the transition state (TS) 2, 31.2 kcal/mol with respect to 1, is 20.8 kcal/mol lower than the reactants at the best G2 level. The TS 2 is found to lie significantly lower and to have much tighter structure than those previously reported. The thermodynamically most stable N
2
O+H
2
O products can be formed from 1 by the complex mechanism (iii), involving 1,3-hydrogen shift from nitrogen to oxygen, rotation of the OH bond, H shift from one oxygen to another and migration of the second H atom from N to O leading to elimination of H
2
O. The rate-determining step is the 1,3-H shift at TS 4 which is 12.5 kcal/mol lower than NH
2
+NO
2
, but 8.3 kcal/mol higher than the barrier for the nitro-nitrite isomerization at TS 2 at the G2 level. N
2
+H
2
O
2
cannot be formed in the reaction, but several channels are shown to produce N
2
+2OH. All of them have as the rate-determining step the second 1,3-hydrogen shift from nitrogen to oxygen at TS 11 or 16, lying by 6.9 kcal/mol higher than NH
2
+NO
2
, and are not expected to compete with the reaction mechanisms producing H
2
NO+NO and N
2
O+H
2
O.
UR - http://www.scopus.com/inward/record.url?scp=0001695399&partnerID=8YFLogxK
U2 - 10.1063/1.470546
DO - 10.1063/1.470546
M3 - Article
AN - SCOPUS:0001695399
SN - 0021-9606
VL - 103
SP - 5640
EP - 5649
JO - The Journal of Chemical Physics
JF - The Journal of Chemical Physics
IS - 13
ER -