Skip to content

Commit e22227a

Browse files
davidfarinajrdavidfarinajr
committed
added halocarbene_recombination training reactions
1 parent b89c436 commit e22227a

File tree

2 files changed

+142
-9
lines changed

2 files changed

+142
-9
lines changed

‎input/kinetics/families/halocarbene_recombination/training/dictionary.txt

+49
Original file line numberDiff line numberDiff line change
@@ -127,3 +127,52 @@ multiplicity 2
127127
3 F u0 p3 c0 {4,S}
128128
4 *1 C u1 p0 c0 {1,S} {2,S} {3,S}
129129

130+
F
131+
multiplicity 2
132+
1 *1 F u1 p3 c0
133+
134+
OH
135+
multiplicity 2
136+
1 *1 O u1 p2 c0 {2,S}
137+
2 H u0 p0 c0 {1,S}
138+
139+
O2
140+
multiplicity 3
141+
1 *1 O u1 p2 c0 {2,S}
142+
2 O u1 p2 c0 {1,S}
143+
144+
CF2O2
145+
multiplicity 3
146+
1 F u0 p3 c0 {5,S}
147+
2 F u0 p3 c0 {5,S}
148+
3 *1 O u0 p2 c0 {4,S} {5,S}
149+
4 O u1 p2 c0 {3,S}
150+
5 *2 C u1 p0 c0 {1,S} {2,S} {3,S}
151+
152+
CHF
153+
1 F u0 p3 c0 {2,S}
154+
2 *2 C u0 p1 c0 {1,S} {3,S}
155+
3 H u0 p0 c0 {2,S}
156+
157+
CHFO2
158+
multiplicity 3
159+
1 F u0 p3 c0 {4,S}
160+
2 *1 O u0 p2 c0 {3,S} {4,S}
161+
3 O u1 p2 c0 {2,S}
162+
4 *2 C u1 p0 c0 {1,S} {2,S} {5,S}
163+
5 H u0 p0 c0 {4,S}
164+
165+
CF3_p
166+
multiplicity 2
167+
1 F u0 p3 c0 {4,S}
168+
2 F u0 p3 c0 {4,S}
169+
3 *1 F u0 p3 c0 {4,S}
170+
4 *2 C u1 p0 c0 {1,S} {2,S} {3,S}
171+
172+
CF2OH
173+
1 F u0 p3 c0 {2,S}
174+
2 *2 C u1 p0 c0 {1,S} {3,S} {4,S}
175+
3 F u0 p3 c0 {2,S}
176+
4 *1 O u0 p2 c0 {2,S} {5,S}
177+
5 H u0 p0 c0 {4,S}
178+

‎input/kinetics/families/halocarbene_recombination/training/reactions.py

+93-9
Original file line numberDiff line numberDiff line change
@@ -13,7 +13,7 @@
1313
label = "CF2 + CH3 <=> CF2CH3",
1414
degeneracy = 1.0,
1515
kinetics = Arrhenius(A=(2.1e+13,'cm^3/(mol*s)'), n=-0.207, Ea=(0,'cal/mol'), T0=(1,'K')),
16-
rank = 3,
16+
rank = 5,
1717
shortDesc = """The chemkin file reaction is CF3-CF2 <=> CF2 + CF3""",
1818
longDesc =
1919
"""
@@ -36,7 +36,7 @@
3636
label = "CF2 + H <=> CHF2",
3737
degeneracy = 1.0,
3838
kinetics = Arrhenius(A=(2.75e+06,'cm^3/(mol*s)'), n=-0.32, Ea=(7696,'cal/mol'), T0=(1,'K')),
39-
rank = 3,
39+
rank = 10,
4040
shortDesc = """The chemkin file reaction is CF2 + H <=> CHF2""",
4141
longDesc =
4242
"""
@@ -50,7 +50,7 @@
5050
label = "C2F5 <=> CF3 + CF2",
5151
degeneracy = 1.0,
5252
kinetics = Arrhenius(A=(4.27e+15,'s^-1'), n=0, Ea=(56240,'cal/mol'), T0=(1,'K')),
53-
rank = 3,
53+
rank = 10,
5454
shortDesc = """The chemkin file reaction is CF3-CF2 <=> CF2 + CF3""",
5555
longDesc =
5656
"""
@@ -64,7 +64,7 @@
6464
label = "CCl2 + Cl <=> CCl3",
6565
degeneracy = 1.0,
6666
kinetics = Arrhenius(A=(1.58e+13,'cm^3/(mol*s)'), n=0, Ea=(0,'cal/mol'), T0=(1,'K')),
67-
rank = 3,
67+
rank = 10,
6868
shortDesc = """The chemkin file reaction is CCL2 + CL <=> CCL3""",
6969
longDesc =
7070
"""
@@ -78,7 +78,7 @@
7878
label = "CCl2 + H <=> CHCl2",
7979
degeneracy = 1.0,
8080
kinetics = Arrhenius(A=(1e+14,'cm^3/(mol*s)'), n=0, Ea=(0,'cal/mol'), T0=(1,'K')),
81-
rank = 3,
81+
rank = 10,
8282
shortDesc = """The chemkin file reaction is CCL2 + H <=> CHCL2""",
8383
longDesc =
8484
"""
@@ -92,7 +92,7 @@
9292
label = "CClF + Cl <=> CCl2F",
9393
degeneracy = 1.0,
9494
kinetics = Arrhenius(A=(1.6e+13,'cm^3/(mol*s)'), n=0, Ea=(0,'cal/mol'), T0=(1,'K')),
95-
rank = 3,
95+
rank = 10,
9696
shortDesc = """The chemkin file reaction is CFCL + CL <=> CFCL2""",
9797
longDesc =
9898
"""
@@ -106,7 +106,7 @@
106106
label = "C2Cl2F3 <=> CF3 + CCl2",
107107
degeneracy = 1.0,
108108
kinetics = Arrhenius(A=(3e+15,'s^-1'), n=0, Ea=(79000,'cal/mol'), T0=(1,'K')),
109-
rank = 3,
109+
rank = 10,
110110
shortDesc = """The chemkin file reaction is CF3CCL2 <=> CF3 + CCL2""",
111111
longDesc =
112112
"""
@@ -120,7 +120,7 @@
120120
label = "C2ClF4 <=> CClF2 + CF2",
121121
degeneracy = 1.0,
122122
kinetics = Arrhenius(A=(4.27e+15,'s^-1'), n=0, Ea=(56240,'cal/mol'), T0=(1,'K')),
123-
rank = 3,
123+
rank = 10,
124124
shortDesc = """The chemkin file reaction is C2F4CL <=> CF2 + CF2CL""",
125125
longDesc =
126126
"""
@@ -134,7 +134,7 @@
134134
label = "C2BrF4 <=> CBrF2 + CF2",
135135
degeneracy = 1.0,
136136
kinetics = Arrhenius(A=(4.27e+15,'s^-1'), n=0, Ea=(56240,'cal/mol'), T0=(1,'K')),
137-
rank = 3,
137+
rank = 10,
138138
shortDesc = """The chemkin file reaction is C2F4BR <=> CF2 + CF2BR""",
139139
longDesc =
140140
"""
@@ -143,3 +143,87 @@
143143
""",
144144
)
145145

146+
entry(
147+
index = 10,
148+
label = "O2 + CF2 <=> CF2O2",
149+
degeneracy = 2.0,
150+
kinetics = Arrhenius(A=(2560.47,'cm^3/(mol*s)'), n=2.72845, Ea=(64.1698,'kJ/mol'), T0=(1,'K'), Tmin=(298,'K'), Tmax=(2500,'K'), comment="""Fitted to 50 data points; dA = *|/ 1.0708, dn = +|- 0.00898775, dEa = +|- 0.048911 kJ/mol"""),
151+
rank = 5,
152+
shortDesc = """M062X-D3/jun-cc-pVTZ RRHO""",
153+
longDesc =
154+
"""
155+
Calculated with Gaussian 16 using M062X with D3 dispersion and jun-cc-pVTZ basis set
156+
barrier = 71.944 kJ/mol
157+
158+
Coordinates (Angstoms):
159+
F -0.746829 1.189537 -0.240732
160+
F -1.545064 -0.687194 0.261703
161+
O 0.870414 -0.603846 0.187929
162+
O 1.76486 0.176978 -0.102154
163+
C -0.665311 0.205825 0.604695
164+
""",
165+
)
166+
167+
entry(
168+
index = 11,
169+
label = "O2 + CHF <=> CHFO2",
170+
degeneracy = 2.0,
171+
kinetics = Arrhenius(A=(47280.1,'cm^3/(mol*s)'), n=2.41746, Ea=(6.84749,'kJ/mol'), T0=(1,'K'), Tmin=(298,'K'), Tmax=(2500,'K'), comment="""Fitted to 50 data points; dA = *|/ 1.05108, dn = +|- 0.00654561, dEa = +|- 0.035621 kJ/mol"""),
172+
rank = 5,
173+
shortDesc = """M062X-D3/jun-cc-pVTZ RRHO""",
174+
longDesc =
175+
"""
176+
Calculated with Gaussian 16 using M062X with D3 dispersion and jun-cc-pVTZ basis set
177+
barrier = 12.781 kJ/mol
178+
179+
Coordinates (Angstoms):
180+
H -0.508707 -0.95089 0.234354
181+
F -1.388965 0.648677 -0.38389
182+
O 1.179152 0.711778 0.316595
183+
O 1.634311 -0.144637 -0.39772
184+
C -0.763631 0.068213 0.60273
185+
""",
186+
)
187+
188+
entry(
189+
index = 12,
190+
label = "CF2 + F <=> CF3_p",
191+
degeneracy = 1.0,
192+
kinetics = Arrhenius(A=(5.18506e+11,'cm^3/(mol*s)'), n=0.4717, Ea=(2.886,'kJ/mol'), T0=(1,'K'), Tmin=(298,'K'), Tmax=(2500,'K')),
193+
rank = 2,
194+
shortDesc = """VRC-TST high-pressure limit""",
195+
longDesc =
196+
"""
197+
VRC-TST CASPT2 aug-cc-pVDZ
198+
Thermal Decomposition of CF3 and the Reaction of CF2 + OH → CF2O + H
199+
N. K. Srinivasan, M.-C. Su, J. V. Michael, A. W. Jasper, S. J. Klippenstein, and L. B. Harding
200+
The Journal of Physical Chemistry A 2008 112 (1), 31-37
201+
DOI: 10.1021/jp076344u
202+
""",
203+
)
204+
205+
entry(
206+
index = 13,
207+
label = "CF2 + OH <=> CF2OH",
208+
degeneracy = 1.0,
209+
kinetics = Arrhenius(A=(3.70189e+10,'cm^3/(mol*s)'), n=0.7539, Ea=(3.775,'kJ/mol'), T0=(1,'K'), Tmin=(298,'K'), Tmax=(2500,'K')),
210+
rank = 2,
211+
shortDesc = """VRC-TST high-pressure limit""",
212+
longDesc =
213+
"""
214+
VRC-TST CASPT2 aug-cc-pVDZ
215+
Thermal Decomposition of CF3 and the Reaction of CF2 + OH → CF2O + H
216+
N. K. Srinivasan, M.-C. Su, J. V. Michael, A. W. Jasper, S. J. Klippenstein, and L. B. Harding
217+
The Journal of Physical Chemistry A 2008 112 (1), 31-37
218+
DOI: 10.1021/jp076344u
219+
220+
We are using rate for CF2 + OH -> CF2O + H
221+
For the CF2 + OH reaction, the CF2O + H product channel is highly exothermic
222+
(55.0 kcal/mol at the QCISD(T)/CBS level). With such a large exothermicity there
223+
should be essentially no collisional stabilization of the CF2OH complex
224+
(69.4 kcal/mol exothermic) except perhaps at very low temperature and extraordinarily high pressures.
225+
226+
We will let the RMG PDEP module skip the CF2OH intermediate
227+
""",
228+
)
229+

0 commit comments

Comments
 (0)