Supporting Information
for the article
Numerical Study of the Superadiabatic Flame Temperature Phenomenon in HN3 Flame
by
*O.P. Korobeinicheva, A.A. Paletskya, T.A.Bolshovaa and V.D Knyazevb
a
b
Institute of Chemical Kinetics and Combustion SB RAS, Novosibirsk, Russia
The Catholic University of America, Washington, D. C., United States of America
1
Table 1S. Kinetics mechanism of HN3 decomposition
(k = A T**b exp(-E/RT)) A units: mole-cm-sec-K, E units Joules/mole
REACTIONS CONSIDERED
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
N3H+N2=N2+NH+N2
N3H+N3H=N2+NH+N3H
N3H+AR=N2+NH+AR
N3H+H=N2+NH2
N3H+N=N2+NNH
N3H+NH=NH2+N3
N3H+NH2=NH3+N3
H+H+M=H2+M
H2
Enhanced
H+H+H2=H2+H2
N2+M=N+N+M
N2
Enhanced
NH+M=N+H+M
NH+H=N+H2
NH+N=N2+H
NH+NH=NH2+N
NH+NH=N2+H2
NH+NH=N2+H+H
NH2+M=NH+H+M
NH+H2=NH2+H
NH2+N=N2+H+H
NH2+NH=N2H2+H
NH2+NH=NH3+N
NH3+NH=NH2+NH2
NH2+NH2=N2H2+H2
NH3+M=NH2+H+M
NH3+M=NH+H2+M
NH3+H=NH2+H2
NH3+NH2=N2H3+H2
NNH=N2+H
NNH+M=N2+H+M
NNH+H=N2+H2
NNH+N=NH+N2
NNH+NH=N2+NH2
NNH+NH2=N2+NH3
NNH+NNH=N2H2+N2
N2H2+M=NNH+H+M
N2
Enhanced
H2
Enhanced
N2H2+M=NH+NH+M
N2
Enhanced
H2
Enhanced
N2H2+H=NNH+H2
N2H2+N=NNH+NH
N2H2+NH=NNH+NH2
N2H2+NH2=NH3+NNH
N2H3+M=NH2+NH+M
N2H3+M=N2H2+H+M
N2H3+H=N2H2+H2
A
by
by
b
E
2.14E+26
6.67E+26
7.55E+25
3.71E+07
1.87E+08
7.83E+02
5.88E+00
6.50E+17
-3.0
-2.9
-3.0
1.9
1.5
3.2
3.5
-1.0
195151.0
201280.0
191551.0
13754.0
14500.0
41700.0
-2900.0
0.0
1.00E+17
1.00E+28
-0.6
-3.3
0.0
942030.0
2.65E+14
3.20E+13
9.00E+11
5.95E+02
1.00E+08
2.54E+13
3.16E+23
1.00E+14
6.90E+13
1.50E+15
1.00E+13
3.16E+14
1.00E+13
2.20E+16
6.30E+14
5.42E+05
1.00E+11
3.00E+08
1.00E+13
1.00E+14
3.00E+13
2.00E+11
1.00E+13
1.00E+13
5.00E+16
0.0
0.0
0.5
2.9
1.0
0.0
-2.0
0.0
0.0
-0.5
0.0
0.0
0.0
0.0
0.0
2.4
0.5
0.0
0.5
0.0
0.0
0.5
0.0
0.0
0.0
316100.0
1360.0
0.0
-8370.0
0.0
0.0
382670.0
84030.0
0.0
0.0
8370.0
112080.0
6280.0
391340.0
391000.0
41530.0
90430.0
0.0
12810.0
0.0
8370.0
8370.0
0.0
16750.0
209340.0
3.16E+16
0.0
416170.0
8.50E+04
1.00E+06
1.00E+13
8.80E-02
5.00E+16
1.00E+17
1.00E+13
2.6
2.0
0.0
4.0
0.0
0.0
0.0
-963.0
0.0
25120.0
-6740.0
251210.0
138160.0
0.0
0.000E+00
5.000E+00
by
by
2.000E+00
2.000E+00
by
by
2.000E+00
2.000E+00
2
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
N2H3+H=NH2+NH2
5.00E+13
0.0
N2H3+H=NH+NH3
1.00E+11
0.0
N2H3+N=N2H2+NH
1.00E+06
2.0
N2H3+NH=N2H2+NH2
2.00E+13
0.0
N2H3+NH2=N2H2+NH3
1.00E+11
0.5
N2H3+NNH=N2H2+N2H2
1.00E+13
0.0
N2H3+N2H3=NH3+NH3+N2
3.00E+12
0.0
N2H3+N2H3=N2H4+N2H2
1.20E+13
0.0
N2H4(+M)=NH2+NH2(+M)
5.00E+14
0.0
Low pressure limit: 0.15000E+16 0.00000E+00 0.16328E+06
N2
Enhanced by
2.400E+00
NH3
Enhanced by
3.000E+00
N2H4
Enhanced by
4.000E+00
N2H4+M=N2H3+H+M
1.00E+15
0.0
N2
Enhanced by
2.400E+00
NH3
Enhanced by
3.000E+00
N2H4
Enhanced by
4.000E+00
N2H4+H=N2H3+H2
7.00E+12
0.0
N2H4+H=NH2+NH3
2.40E+09
0.0
N2H4+N=N2H3+NH
1.00E+10
1.0
N2H4+NH=NH2+N2H3
1.00E+09
1.5
N2H4+NH2=N2H3+NH3
1.80E+06
1.7
N3+N3=N2+N2+N2
8.43E+11
0.0
H+N3=N2+NH
6.03E+13
0.0
N3+N=N2+N2
8.43E+13
0.0
8370.0
0.0
0.0
0.0
0.0
16750.0
0.0
0.0
251210.0
266280.0
10470.0
12980.0
8370.0
8370.0
-5780.0
0.0
0.0
0.0
3
Table 2S. Results of the quantum chemical study. Units are Å, amu, hartree, and cm-1.
hn3
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N
X
Y
7
-1.706458
-2.322950
1
-2.603872
-2.190261
7
-0.810269
-1.879217
7
0.094694
-1.522562
N
X
Y
7
-0.023544
0.000073
1
-0.002753
0.000023
7
1.171020
-0.000173
7
2.182935
-0.001512
Electronic energy (hartree):
Z
-0.066073
0.386900
0.660744
1.211232
Z
-0.001217
1.024502
-0.406034
-0.932441
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
-164.7059545
-164.4115719
-164.5505160
CCSD/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
-164.3881483
-164.4150842
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
555
3606 634 1246 1356 2391 CCSD/aug-cc-pvdz[Opt]
504
3499
575 1180 1315 2234 -
-
h_hn3_2
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N X
Y
7
1.102971
-0.340121
1
1.634233
0.358120
7
-0.053258
-0.416761
7
-1.080145
-0.732823
1
2.049278
-1.734053
-
Electronic energy (hartree):
Z
-0.089828
-0.595311
-0.551534
-0.877814
-0.323691
-
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
-
-165.1982569
CCSD/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
-
Barrier width
1.5565676
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
-954
1216 347
1349 485
2314 575
3625 665 -
-
-
n_hn3_1
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N X
Y
7
2.010879
-0.248341
7
0.955204
0.065514
7
-0.011866
0.421508
1
2.007258
-1.540181
7
1.909707
-2.733608
-
Electronic energy (hartree):
Z
-0.521358
-1.028341
-1.502013
-0.348293
-0.229858
-
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
CCSD/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
-219.2540176
-218.8587230
-219.0291815
-
Barrier width
0.9160000
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
124
1099 494
1356 622
2108 661
-2281 735 -
-
-
n_hn3_2
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N X
Y
7
-1.505783
-2.497576
1
-2.442477
-2.667215
7
-0.916439
-1.638695
7
0.032458
-1.292811
7
-0.793466
-4.207487
Electronic energy (hartree):
Z
-0.071051
0.275842
0.683738
1.220495
-0.099963
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
CCSD/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
-219.2496336
-218.8568686
-219.0247802
-
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
-713
1044 160
1294 460
2022 495
3504 565 -
4
n_hn3_3
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N X
Y
7
-1.878382
-1.829296
1
-2.362847
-2.679099
7
-0.693578
-2.135091
7
0.309036
-1.618969
7
-0.479411
-3.794201
Electronic energy (hartree):
Z
0.295537
0.027056
0.626188
1.012083
0.466229
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
CCSD/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
-219.2217627
-218.8279226
-218.9954454
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
379
1384 452
1645 530
3584 652
-920 1162 -
-219.2511860
-218.8566856
-219.0262522
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
-772
1279 197
1298 243
1940 612
3583 639 -
-
n_hn3_4
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N X
Y
7
-0.702392
-0.266554
1
-1.594370
0.196080
7
-0.601042
-1.260260
7
-0.028628
-2.193256
7
1.535557
-2.346723
Electronic energy (hartree):
Z
0.784730
0.925780
1.507759
1.916252
1.149526
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
CCSD/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
-
n3
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N
X
Y
7
-1.684422
-2.214041
7
-0.788677
-1.879702
7
0.107458
-1.543966
Electronic energy (hartree):
Z
-0.080242
0.591313
1.262012
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
-164.0651137
-163.7673419
-163.8995360
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
510 633 1456 1728 -
n2
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N
X
Y
7
0.000000 0.000000
7
0.000000 0.000000
Electronic energy (hartree):
Z
0.545239
-0.545239
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
-109.4827318
-109.2927886
-109.3803583
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
2586 -
-55.2097946
-55.1055657
-55.1451107
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
3387 -
nh
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N
X
Y
7 -0.228139 0.329319
1 -0.617555 1.288335
Electronic energy (hartree):
Z
0.000000
0.000000
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
nh2
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N
X
Y
7 -0.233123 0.333362
1 -0.612708 1.282105
1
0.778305 0.479003
Electronic energy (hartree):
Z
0.000000
0.000000
0.000000
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
-55.8589788
-55.7515947
-
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
1562 3484 3579 -
5
hn2
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N
X
Y
7
-1.663195
-2.374856
1
-2.613410
-2.236869
7
-0.856767
-1.580019
Electronic energy (hartree):
Z
0.022341
0.432509
0.311898
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
-109.9870695
-109.7855721
-109.8742071
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
1145 1975 3047 -
nh2_hn3_01
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N X
Y
7
1.607868
-0.412746
7
1.172506
-0.130162
7
0.752344
0.206485
1
2.072061
-1.523122
7
2.151989
-2.797767
1
1.981652
-3.098026
1
1.377313
-3.162446
Electronic energy (hartree):
Z
-0.064990
-1.164312
-2.157440
-0.025595
-0.079546
-1.036203
0.469102
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
-220.5560701
-220.1570836
-
CCSD/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
-
Barrier width
0.7027000
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
-2191
630
1433
80
719
1591
134
741
2235
423
1173
3540
530
1369
3639
-
-
-
nh2_hn3_02
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N X
Y
7
-2.390141
-4.483745
1
-2.409975
-5.492715
7
-2.631509
-3.994644
7
-2.455769
-3.248017
7
-0.638388
-4.291570
1
-0.225558
-3.761106
1
-0.905682
-3.584836
Electronic energy (hartree):
Z
0.515325
0.561830
1.668493
2.513343
-0.221254
0.542984
-0.900607
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
-220.5395300
-220.1431575
-
CCSD/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
-
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
-790
644
1564
121
838
2133
190
937
3533
483
1089
3632
511
1363
3658
-
-
-
nh2_hn3_04
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N X
Y
7
-1.469754
-2.442214
1
-2.141690
-2.289311
7
-0.384739
-2.808879
7
0.752612
-3.007981
7
1.466966
-2.206627
1
2.440077
-2.404734
1
1.339307
-1.228997
Electronic energy (hartree):
Z
1.954357
2.699345
2.437027
2.358065
0.882422
1.098599
1.138486
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
-220.5399100
-220.1417915
-
CCSD/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
-
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
-661
625
1564
126
883
1982
198
925
3526
438
1275
3582
576
1326
3632
-
-
-
6
nh3
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N
X
Y
7
-0.326768
0.333321
1
-0.642533
1.146389
1
0.681352
0.332325
1
-0.644543
-0.478587
Electronic energy (hartree):
Z
-0.033723
-0.540309
-0.065660
-0.540900
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
CCSD/aug-cc-pvdz[Opt]
-56.5305369
-56.4249954
-56.4804577
-
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
1044
3720 1693 1694 3588 3720 -
hn3_ar_vdw01
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N
X
Y
7
-0.691015
0.179463
1
-0.273725
1.083969
7
-1.922392
0.284774
7
-3.038841
0.236043
18
1.709333
3.132014
N
X
Y
7
1.174069
0.878088
1
0.281006
0.374015
7
2.096761
0.018498
7
3.039813 -0.622743
18
-2.469750 -0.127273
Electronic energy (hartree):
Z
-0.494832
-0.304913
-0.488047
-0.511388
0.103180
Z
-0.000719
0.007429
0.000295
-0.000299
-0.000132
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
-692.2438213
-691.3824559
-
CCSD/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
-691.3563365
-691.3860023
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
26
1247 40
1359 58
2390 557
3607 634 CCSD/aug-cc-pvdz[Opt]
10
1180
51
1317
108
2236
505
3510
576 -
-
hn3_ar_vdw02
Structures
BH&HLYP/aug-cc-pvdz[Opt]
N
X
Y
7
-0.628971 0.165343
1
-0.314412 1.111210
7
-1.864528 0.143001
7
-2.969501 0.019615
18
-1.553831 3.828000
N
X
Y
7
0.044913 0.000000
1
0.179743 0.000000
7
1.188344 0.000000
7
2.138326 0.000000
18
2.598803 0.000000
Electronic energy (hartree):
Z
-0.494702
-0.308218
-0.513562
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
-0.557945
0.202038
Z
0.161893
1.178845
-0.369644
-1.000883
2.921386
CCSD/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
-692.2438163
-691.3826030
-
-691.3565038
-691.3862001
Vibrational frequencies (cm^-1)
BH&HLYP/aug-cc-pvdz[Opt]
18
1248 35
1358 102
2390 555
3604 634
-
CCSD/aug-cc-pvdz[Opt]
28
1181
58
1316
74
2234
503
3502
574 -
-
-
7
n
Electronic energy (hartree):
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
-54.5812562
-54.4869816
-54.5169239
h
Electronic energy (hartree):
BH&HLYP/aug-cc-pvdz[Opt]
-0.4980784
ar
Electronic energy (hartree):
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
CCSD/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
-527.5375827
-526.9696846
-526.9671591
-526.9696846
Table 3S. Reaction energy barriers and Ho0 (kJ mol-1, ZPE included).
HN3+H=N2+NH2
BH&HLYP/aug-cc-pvdz[Opt]
Final model (fitted to experiment)
Energy barrier
19.87
23.57
Ho0
-352.95
-323.33
HN3+N=N2+NNH (Attack on the 2-nd atom (N))
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
Final model (fitted to experiment)
Energy barrier
99.58
110.36
112.92
18.60
Ho0
-485.57
-478.26
-497.48
HN3+N=Products (Attack on the 3-rd atom (N))
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
Energy barrier
171.84
185.45
189.03
Ho0
8
HN3+N=N2+NNH (Attack on the 4-th atom (N))
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
Energy barrier
94.61
109.95
108.16
Ho0
-485.57
-478.26
-497.48
HN3+N=NH+N3 (Attack on the 1-st atom (H))
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
CCSD(T)/aug-cc-pvtz
Energy barrier
71.67
89.10
84.97
Ho0
16.11
51.15
43.66
Energy barrier
22.22
14.92
14.92
Ho0
-76.22
-72.16
-72.16
HN3+NH2=NH3+N3
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
Final model
HN3+NH2=Products (Attack on the 2-nd atom (N))
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
Energy barrier
80.34
66.18
Ho0
HN3+NH2=Products (Attack on the 4-th atom (N))
BH&HLYP/aug-cc-pvdz[Opt]
CCSD(T)/aug-cc-pvdz
Energy barrier
79.13
69.55
Ho0
Comments on individual reactions
N + HN3 → Products
Two channels are possible:
N + HN3 → NH + N3
N + HN3 → N2H + N2 → H + N2 + N2
The first channel results from an abstraction of H atom by N. The second channel can result from
N atom attack on the N of HN3 nearest to H (HN(…N)NN) or the farthest from H
9
(HNNN(…N)). There is only one experimental study of this reaction, performed by Le Bras and
Combourieu [1]. The rate constant obtained at 298 K was 2.7×109 cm3 mol-1 s-1. The energy
barriers obtained in quantum chemical calculations are large. The room temperature overall rate
constant calculated using transition state theory and the above results is much lower than the
experimental value of Le Bras and Combourieu, with many orders of magnitude difference. In
modeling, the energy of the transition state of the second channel were fitted to reproduce the
rate constant of Le Bras and Combourieu. The first channel was not used because of the
endothermicity exceeding the barrier required for fitting the experimental rate constant.
NH2 + HN3 → Products
No experimental data are available for this reaction. An earlier computational study was
performed by Henon and Bohr [2]. In the current work, quantum chemical calculations were
performed for the reaction of N atoms with HN3. The methods were BH&HLYP/aug-cc-pvdz for
geometry optimization and vibrational frequencies and CCSD(T)/aug-cc-pvtz for single-point
energy calculations. Radical attack on the H atom (atom 1) and nitrogen atoms 2 and 4 were
studied. Energy barrier for attack on H (producing NH3 + N3) is only 14.9 kJ mol-1, whereas
those for the other two reaction channels are 66.2 and 69.6 kJ mol-1, making these two channels
unimportant. Rate constants obtained in transition state theory calculations are larger than those
derived by Henon and Bohr by approximately two orders of magnitude, due to the lower energy
barrier but also due to the fact that calculations performed in that earlier study did not include the
partition function of the hindered internal rotation about the forming H2N-H bond, as described
in their article, which resulted in too low rate constant values.
References
[1] G. Le Bras, J. Combourieu, Int. J. Chem. Kinet. 5 (1973) 559-576.
[2] E. Henon, F. Bohr, J. Molec. Struc. - Theochem. 531 (2000) 283-299.
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