diff --git a/input/kinetics/families/H_Abstraction/training/reactions.py b/input/kinetics/families/H_Abstraction/training/reactions.py index 9c160c8e97..1be54db295 100644 --- a/input/kinetics/families/H_Abstraction/training/reactions.py +++ b/input/kinetics/families/H_Abstraction/training/reactions.py @@ -1516,9 +1516,9 @@ label = "CH3CH2NH2_1 + H <=> CH2CH2NH2 + H2", degeneracy = 3, kinetics = Arrhenius( - A = (9.07e+04, 'cm^3/(mol*s)'), - n = 2.75, - Ea = (6800, 'cal/mol'), + A = (1.6e+13, 'cm^3/(mol*s)'), + n = 0, + Ea = (8174, 'cal/mol'), T0 = (1, 'K'), Tmin = (700, 'K'), Tmax = (2000, 'K'), @@ -1528,6 +1528,7 @@ longDesc = u""" CBS-QB3 +doi: 10.1016/j.combustflame.2015.10.032 """, ) @@ -1536,9 +1537,9 @@ label = "CH3CH2NH2_2 + H <=> CH3CHNH2 + H2", degeneracy = 2, kinetics = Arrhenius( - A = (9.54e+03, 'cm^3/(mol*s)'), - n = 2.94, - Ea = (500, 'cal/mol'), + A = (1.16e+13, 'cm^3/(mol*s)'), + n = 0, + Ea = (3585, 'cal/mol'), T0 = (1, 'K'), Tmin = (700, 'K'), Tmax = (2000, 'K'), @@ -1548,6 +1549,7 @@ longDesc = u""" CBS-QB3 +doi: 10.1016/j.combustflame.2015.10.032 """, ) @@ -1556,9 +1558,9 @@ label = "CH3CH2NH2_3 + H <=> CH3CH2NH + H2", degeneracy = 2, kinetics = Arrhenius( - A = (8.04e+04, 'cm^3/(mol*s)'), - n = 2.64, - Ea = (5500, 'cal/mol'), + A = (5.47e+12, 'cm^3/(mol*s)'), + n = 0, + Ea = (6907, 'cal/mol'), T0 = (1, 'K'), Tmin = (700, 'K'), Tmax = (2000, 'K'), @@ -1568,6 +1570,7 @@ longDesc = u""" CBS-QB3 +doi: 10.1016/j.combustflame.2015.10.032 """, ) @@ -1576,9 +1579,9 @@ label = "CH3CH2NH2_1 + CH3_r3 <=> CH2CH2NH2 + CH4", degeneracy = 3, kinetics = Arrhenius( - A = (3.28e-04, 'cm^3/(mol*s)'), - n = 4.85, - Ea = (7000, 'cal/mol'), + A = (6.00e+12, 'cm^3/(mol*s)'), + n = 0, + Ea = (12620, 'cal/mol'), T0 = (1, 'K'), Tmin = (700, 'K'), Tmax = (2000, 'K'), @@ -1588,6 +1591,7 @@ longDesc = u""" CBS-QB3 +doi: 10.1016/j.combustflame.2015.10.032 """, ) @@ -1596,9 +1600,9 @@ label = "CH3CH2NH2_2 + CH3_r3 <=> CH3CHNH2 + CH4", degeneracy = 2, kinetics = Arrhenius( - A = (2.76e-02, 'cm^3/(mol*s)'), - n = 4.23, - Ea = (4200, 'cal/mol'), + A = (1.23e+13, 'cm^3/(mol*s)'), + n = 0, + Ea = (7911, 'cal/mol'), T0 = (1, 'K'), Tmin = (700, 'K'), Tmax = (2000, 'K'), @@ -1608,6 +1612,7 @@ longDesc = u""" CBS-QB3 +doi: 10.1016/j.combustflame.2015.10.032 """, ) @@ -1616,9 +1621,9 @@ label = "CH3CH2NH2_3 + CH3_r3 <=> CH3CH2NH + CH4", degeneracy = 2, kinetics = Arrhenius( - A = (1.27e-02, 'cm^3/(mol*s)'), - n = 4.41, - Ea = (4800, 'cal/mol'), + A = (2.23e+12, 'cm^3/(mol*s)'), + n = 0, + Ea = (9441, 'cal/mol'), T0 = (1, 'K'), Tmin = (700, 'K'), Tmax = (2000, 'K'), @@ -1628,6 +1633,7 @@ longDesc = u""" CBS-QB3 +doi: 10.1016/j.combustflame.2015.10.032 """, ) @@ -1636,9 +1642,9 @@ label = "CH3CH2NH2_1 + NH2 <=> CH2CH2NH2 + NH3", degeneracy = 3, kinetics = Arrhenius( - A = (1.44e-02, 'cm^3/(mol*s)'), - n = 4.43, - Ea = (3600, 'cal/mol'), + A = (9.21e+12, 'cm^3/(mol*s)'), + n = 0, + Ea = (9393, 'cal/mol'), T0 = (1, 'K'), Tmin = (700, 'K'), Tmax = (2000, 'K'), @@ -1648,6 +1654,7 @@ longDesc = u""" CBS-QB3 +doi: 10.1016/j.combustflame.2015.10.032 """, ) @@ -1656,9 +1663,9 @@ label = "CH3CH2NH2_2 + NH2 <=> CH3CHNH2 + NH3", degeneracy = 2, kinetics = Arrhenius( - A = (1.28e+00, 'cm^3/(mol*s)'), - n = 3.75, - Ea = (1000, 'cal/mol'), + A = (8.01e+12, 'cm^3/(mol*s)'), + n = 0, + Ea = (4493, 'cal/mol'), T0 = (1, 'K'), Tmin = (700, 'K'), Tmax = (2000, 'K'), @@ -1668,6 +1675,7 @@ longDesc = u""" CBS-QB3 +doi: 10.1016/j.combustflame.2015.10.032 """, ) @@ -1676,9 +1684,9 @@ label = "CH3CH2NH2_3 + NH2 <=> CH3CH2NH + NH3", degeneracy = 2, kinetics = Arrhenius( - A = (9.73e-02, 'cm^3/(mol*s)'), - n = 4.03, - Ea = (1900, 'cal/mol'), + A = (2.14e+12, 'cm^3/(mol*s)'), + n = 0, + Ea = (5927, 'cal/mol'), T0 = (1, 'K'), Tmin = (700, 'K'), Tmax = (2000, 'K'), @@ -1688,6 +1696,7 @@ longDesc = u""" CBS-QB3 +doi: 10.1016/j.combustflame.2015.10.032 """, ) @@ -1709,7 +1718,8 @@ u""" S. Li, E. Dames, D.F. Davidson, R.K. Hanson "High-Temperature Measurements of the Reactions of OH with Ethylamine and Dimethylamine" -The Journal of Physical Chemistry A, 2014, 118, 70-77, http://dx.doi.org/10.1021/jp411141w +The Journal of Physical Chemistry A, 2014, 118, 70-77 +doi: 10.1021/jp411141w (with geometries from http://dx.doi.org/10.1021/ct7002786 CCSD(T)/6-311++G(2d,2p) single-point calculations) """, ) @@ -1732,7 +1742,8 @@ u""" S. Li, E. Dames, D.F. Davidson, R.K. Hanson "High-Temperature Measurements of the Reactions of OH with Ethylamine and Dimethylamine" -The Journal of Physical Chemistry A, 2014, 118, 70-77, http://dx.doi.org/10.1021/jp411141w +The Journal of Physical Chemistry A, 2014, 118, 70-77 +doi: 10.1021/jp411141w (with geometries from http://dx.doi.org/10.1021/ct7002786 CCSD(T)/6-311++G(2d,2p) single-point calculations) """, ) @@ -1755,7 +1766,8 @@ u""" S. Li, E. Dames, D.F. Davidson, R.K. Hanson "High-Temperature Measurements of the Reactions of OH with Ethylamine and Dimethylamine" -The Journal of Physical Chemistry A, 2014, 118, 70-77, http://dx.doi.org/10.1021/jp411141w +The Journal of Physical Chemistry A, 2014, 118, 70-77 +doi: 10.1021/jp411141w (with geometries from http://dx.doi.org/10.1021/ct7002786 CCSD(T)/6-311++G(2d,2p) single-point calculations) """, ) diff --git a/input/kinetics/libraries/Ethylamine/reactions.py b/input/kinetics/libraries/Ethylamine/reactions.py index cdbbce592a..33cfeaeeb8 100644 --- a/input/kinetics/libraries/Ethylamine/reactions.py +++ b/input/kinetics/libraries/Ethylamine/reactions.py @@ -7,13 +7,20 @@ Automated Reaction Mechanism Generation Including Heteroatoms: Nitrogen Alon Grinberg Dana, Beat Buesser, Shamel S. Merchant, William H. Green Table 2 -Kinetic data for reactions 1-9, 13-24 were calculated using: +Kinetic data for reactions marked as `BB` were calculated by B. Buesser with support by A. Vandeputte using: CBS-QB3 for energy barriers, B3LYP/6-311G(2d,d,p) for partition functions, hybrid meta-GGA BMK/6-311G(2d,d,p) for addition reactions. -Kinetic data for reactions 10-12 (NCC + OH) were adopted from the literature (VTST): +Kinetic data for reactions marked as `MA` (NCC + H/CH3/NH2) were adopted from the literature: +M. Altarawneh, M.H. Almatarneh, A. Marashdeh, B.Z. Dlugogorski +"Decomposition of ethylamine through bimolecular reactions" +Combust. Flame 163 (2016) 532–539 +doi: 10.1016/j.combustflame.2015.10.032 + +Kinetic data for reactions marked as "SL" (NCC + OH) were adopted from the literature: S. Li, E. Dames, D.F. Davidson, R.K. Hanson "High-Temperature Measurements of the Reactions of OH with Ethylamine and Dimethylamine" -The Journal of Physical Chemistry A, 2014, 118, 70-77, http://dx.doi.org/10.1021/jp411141w +The Journal of Physical Chemistry A, 2014, 118, 70-77 +doi: 10.1021/jp411141w (with geometries from http://dx.doi.org/10.1021/ct7002786 CCSD(T)/6-311++G(2d,2p) single-point calculations) """ @@ -21,72 +28,72 @@ index = 1, label = "NCC + H <=> CH2CH2NH2 + H2", degeneracy = 1, - kinetics = Arrhenius(A=(9.07e+04, 'cm^3/(mol*s)'), n=2.75, Ea=(6800, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R1: EA H abstraction""", + kinetics = Arrhenius(A=(1.60e+13, 'cm^3/(mol*s)'), n=0, Ea=(8174, 'cal/mol'), T0=(1, 'K')), + shortDesc = u"""Table 2, R1: EA H abstraction; MA""", ) entry( index = 2, label = "NCC + H <=> CH3CHNH2 + H2", degeneracy = 1, - kinetics = Arrhenius(A=(9.54e+03, 'cm^3/(mol*s)'), n=2.94, Ea=(500, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R2: EA H abstraction""", + kinetics = Arrhenius(A=(1.16e+13, 'cm^3/(mol*s)'), n=0, Ea=(3585, 'cal/mol'), T0=(1, 'K')), + shortDesc = u"""Table 2, R2: EA H abstraction; MA""", ) entry( index = 3, label = "NCC + H <=> CH3CH2NH + H2", degeneracy = 1, - kinetics = Arrhenius(A=(8.04e+04, 'cm^3/(mol*s)'), n=2.64, Ea=(5500, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R3: EA H abstraction""", + kinetics = Arrhenius(A=(5.47e+12, 'cm^3/(mol*s)'), n=0, Ea=(6907, 'cal/mol'), T0=(1, 'K')), + shortDesc = u"""Table 2, R3: EA H abstraction; MA""", ) entry( index = 4, label = "NCC + CH3 <=> CH2CH2NH2 + CH4", degeneracy = 1, - kinetics = Arrhenius(A=(3.28e-04, 'cm^3/(mol*s)'), n=4.85, Ea=(7000, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R4: EA H abstraction""", + kinetics = Arrhenius(A=(6.00e+12, 'cm^3/(mol*s)'), n=0, Ea=(12620, 'cal/mol'), T0=(1, 'K')), + shortDesc = u"""Table 2, R4: EA H abstraction; MA""", ) entry( index = 5, label = "NCC + CH3 <=> CH3CHNH2 + CH4", degeneracy = 1, - kinetics = Arrhenius(A=(2.76e-02, 'cm^3/(mol*s)'), n=4.23, Ea=(4200, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R5: EA H abstraction""", + kinetics = Arrhenius(A=(1.23e+13, 'cm^3/(mol*s)'), n=0, Ea=(7911, 'cal/mol'), T0=(1, 'K')), + shortDesc = u"""Table 2, R5: EA H abstraction; MA""", ) entry( index = 6, label = "NCC + CH3 <=> CH3CH2NH + CH4", degeneracy = 1, - kinetics = Arrhenius(A=(1.27e-02, 'cm^3/(mol*s)'), n=4.41, Ea=(4800, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R6: EA H abstraction""", + kinetics = Arrhenius(A=(2.23e+12, 'cm^3/(mol*s)'), n=0, Ea=(9441, 'cal/mol'), T0=(1, 'K')), + shortDesc = u"""Table 2, R6: EA H abstraction; MA""", ) entry( index = 7, label = "NCC + NH2 <=> CH2CH2NH2 + NH3", degeneracy = 1, - kinetics = Arrhenius(A=(1.44e-02, 'cm^3/(mol*s)'), n=4.43, Ea=(3600, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R7: EA H abstraction""", + kinetics = Arrhenius(A=(9.21e+12, 'cm^3/(mol*s)'), n=0, Ea=(9393, 'cal/mol'), T0=(1, 'K')), + shortDesc = u"""Table 2, R7: EA H abstraction; MA""", ) entry( index = 8, label = "NCC + NH2 <=> CH3CHNH2 + NH3", degeneracy = 1, - kinetics = Arrhenius(A=(1.28e+00, 'cm^3/(mol*s)'), n=3.75, Ea=(1000, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R8: EA H abstraction""", + kinetics = Arrhenius(A=(8.01e+12, 'cm^3/(mol*s)'), n=0, Ea=(4493, 'cal/mol'), T0=(1, 'K')), + shortDesc = u"""Table 2, R8: EA H abstraction; MA""", ) entry( index = 9, label = "NCC + NH2 <=> CH3CH2NH + NH3", degeneracy = 1, - kinetics = Arrhenius(A=(9.73e-02, 'cm^3/(mol*s)'), n=4.03, Ea=(1900, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R9: EA H abstraction""", + kinetics = Arrhenius(A=(2.14e+12, 'cm^3/(mol*s)'), n=0, Ea=(5927, 'cal/mol'), T0=(1, 'K')), + shortDesc = u"""Table 2, R9: EA H abstraction; MA""", ) entry( @@ -94,7 +101,7 @@ label = "NCC + OH <=> CH2CH2NH2 + H2O", degeneracy = 1, kinetics = Arrhenius(A=(7.94e+02, 'cm^3/(mol*s)'), n=2.97, Ea=(-1040, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R10: EA H abstraction""", + shortDesc = u"""Table 2, R10: EA H abstraction; SL""", ) entry( @@ -102,7 +109,7 @@ label = "NCC + OH <=> CH3CHNH2 + H2O", degeneracy = 1, kinetics = Arrhenius(A=(3.28e+05, 'cm^3/(mol*s)'), n=2.24, Ea=(-3040, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R11: EA H abstraction""", + shortDesc = u"""Table 2, R11: EA H abstraction; SL""", ) entry( @@ -110,7 +117,7 @@ label = "NCC + OH <=> CH3CH2NH + H2O", degeneracy = 1, kinetics = Arrhenius(A=(1.12e+05, 'cm^3/(mol*s)'), n=2.36, Ea=(-2860, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R12: EA H abstraction""", + shortDesc = u"""Table 2, R12: EA H abstraction; SL""", ) entry( @@ -118,7 +125,7 @@ label = "N2H4 + H <=> N2H3 + H2", degeneracy = 1, kinetics = Arrhenius(A=(1.48e+08, 'cm^3/(mol*s)'), n=1.69, Ea=(4000, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R13: H abstraction""", + shortDesc = u"""Table 2, R13: H abstraction; BB""", ) entry( @@ -126,7 +133,7 @@ label = "N2H4 + CH3 <=> N2H3 + CH4", degeneracy = 1, kinetics = Arrhenius(A=(1.77e+01, 'cm^3/(mol*s)'), n=3.60, Ea=(3500, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R14: H abstraction""", + shortDesc = u"""Table 2, R14: H abstraction; BB""", ) entry( @@ -134,7 +141,7 @@ label = "N2H4 + NH2 <=> N2H3 + NH3", degeneracy = 1, kinetics = Arrhenius(A=(2.59e+03, 'cm^3/(mol*s)'), n=2.83, Ea=(700, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R15: H abstraction""", + shortDesc = u"""Table 2, R15: H abstraction; BB""", ) entry( @@ -142,7 +149,7 @@ label = "CH3CHNH + H <=> CH2CHNH + H2", degeneracy = 1, kinetics = Arrhenius(A=(3.98e+04, 'cm^3/(mol*s)'), n=2.76, Ea=(4400, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R16: H abstraction""", + shortDesc = u"""Table 2, R16: H abstraction; BB""", ) entry( @@ -150,7 +157,7 @@ label = "CH3CHNH + H <=> CH3CHN + H2", degeneracy = 1, kinetics = Arrhenius(A=(1.19e+07, 'cm^3/(mol*s)'), n=1.96, Ea=(2400, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R17: H abstraction""", + shortDesc = u"""Table 2, R17: H abstraction; BB""", ) entry( @@ -158,7 +165,7 @@ label = "CH2CHNH2 + H <=> CH2CH2NH2", degeneracy = 1, kinetics = Arrhenius(A=(3.14e+07, 'cm^3/(mol*s)'), n=1.77, Ea=(3729, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R18: beta scission""", + shortDesc = u"""Table 2, R18: beta scission; BB""", ) entry( @@ -166,7 +173,7 @@ label = "C2H4 + NH2 <=> CH2CH2NH2", degeneracy = 1, kinetics = Arrhenius(A=(1.23e+03, 'cm^3/(mol*s)'), n=2.76, Ea=(1658, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R19: beta scission""", + shortDesc = u"""Table 2, R19: beta scission; BB""", ) entry( @@ -174,7 +181,7 @@ label = "CH3CHNH2 <=> CH2CHNH2 + H", degeneracy = 1, kinetics = Arrhenius(A=(1.14e+09, 's^-1'), n=1.49, Ea=(35100, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R20: beta scission""", + shortDesc = u"""Table 2, R20: beta scission; BB""", ) entry( @@ -182,7 +189,7 @@ label = "CH2NH + H <=> CH2NH2", degeneracy = 1, kinetics = Arrhenius(A=(1.48e+08, 'cm^3/(mol*s)'), n=1.67, Ea=(2.295, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R21: beta scission""", + shortDesc = u"""Table 2, R21: beta scission; BB""", ) entry( @@ -190,7 +197,7 @@ label = "CH2CHNH <=> CH2CNH + H", degeneracy = 1, kinetics = Arrhenius(A=(2.18e+07, 's^-1'), n=2.26, Ea=(50300, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R22: beta scission""", + shortDesc = u"""Table 2, R22: beta scission; BB""", ) entry( @@ -198,7 +205,7 @@ label = "CH3CHN <=> CH3 + HCN", degeneracy = 1, kinetics = Arrhenius(A=(7.52e+10, 's^-1'), n=1.10, Ea=(26200, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R23: beta scission""", + shortDesc = u"""Table 2, R23: beta scission; BB""", ) entry( @@ -206,7 +213,7 @@ label = "CH3CHN <=> CH3CN + H", degeneracy = 1, kinetics = Arrhenius(A=(1.49e+09, 's^-1'), n=1.44, Ea=(27000, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R24: beta scission""", + shortDesc = u"""Table 2, R24: beta scission; BB""", ) entry( @@ -214,7 +221,7 @@ label = "CH2CH2NH2 <=> CH3CHNH2", degeneracy = 1, kinetics = Arrhenius(A=(3.12e+04, 's^-1'), n=2.33, Ea=(31800, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R25: intra H transfer""", + shortDesc = u"""Table 2, R25: intra H transfer; BB""", ) entry( @@ -222,7 +229,7 @@ label = "CH2CHNH <=> CH3CHN", degeneracy = 1, kinetics = Arrhenius(A=(9.20e+05, 's^-1'), n=2.16, Ea=(37400, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R26: intra H transfer""", + shortDesc = u"""Table 2, R26: intra H transfer; BB""", ) entry( @@ -230,6 +237,6 @@ label = "NCC <=> C2H4 + NH3", degeneracy = 1, kinetics = Arrhenius(A=(4.90e+04, 's^-1'), n=2.65, Ea=(65100, 'cal/mol'), T0=(1, 'K')), - shortDesc = u"""Table 2, R27: 1,2-elimination""", + shortDesc = u"""Table 2, R27: 1,2-elimination; BB""", )