From ccdacdaa8997bea151b019b93c3418a0e04c9ed8 Mon Sep 17 00:00:00 2001 From: Bjarne Kreitz Date: Fri, 28 Jun 2024 10:33:38 -0400 Subject: [PATCH] add training rxn --- .../training/dictionary.txt | 136 ++++++++++++ .../training/reactions.py | 196 ++++++++++++++++++ 2 files changed, 332 insertions(+) diff --git a/input/kinetics/families/Surface_Dissociation_Beta_vdW/training/dictionary.txt b/input/kinetics/families/Surface_Dissociation_Beta_vdW/training/dictionary.txt index e69de29bb2..737e6cb089 100755 --- a/input/kinetics/families/Surface_Dissociation_Beta_vdW/training/dictionary.txt +++ b/input/kinetics/families/Surface_Dissociation_Beta_vdW/training/dictionary.txt @@ -0,0 +1,136 @@ +X_5 +1 *5 X u0 p0 c0 + +COOH* +1 *2 O u0 p2 c0 {3,S} {4,S} +2 O u0 p2 c0 {3,D} +3 *1 C u0 p0 c0 {1,S} {2,D} {5,S} +4 *3 H u0 p0 c0 {1,S} +5 *4 X u0 p0 c0 {3,S} + +CO2_2* +1 *2 O u0 p2 c0 {3,D} +2 O u0 p2 c0 {3,D} +3 *1 C u0 p0 c0 {1,D} {2,D} +4 *4 X u0 p0 c0 + +H* +1 *5 X u0 p0 c0 {2,S} +2 *3 H u0 p0 c0 {1,S} + +HCOO* +1 *1 O u0 p2 c0 {3,S} {5,S} +2 O u0 p2 c0 {3,D} +3 *2 C u0 p0 c0 {1,S} {2,D} {4,S} +4 *3 H u0 p0 c0 {3,S} +5 *4 X u0 p0 c0 {1,S} + +CO2* +1 *1 O u0 p2 c0 {3,D} +2 O u0 p2 c0 {3,D} +3 *2 C u0 p0 c0 {1,D} {2,D} +4 *4 X u0 p0 c0 + +HCOOH* +1 O u0 p2 c0 {3,S} {5,S} +2 *1 O u0 p2 c0 {3,D} +3 *2 C u0 p0 c0 {1,S} {2,D} {4,S} +4 H u0 p0 c0 {3,S} +5 H u0 p0 c0 {1,S} +6 *4 X u0 p0 c0 + +CH3O2_2* +1 O u0 p2 c0 {3,S} {6,S} +2 *1 O u0 p2 c0 {3,S} {7,S} +3 *2 C u0 p0 c0 {1,S} {2,S} {4,S} {5,S} +4 *3 H u0 p0 c0 {3,S} +5 H u0 p0 c0 {3,S} +6 H u0 p0 c0 {1,S} +7 *4 X u0 p0 c0 {2,S} + +CH3O2* +1 *3 O u0 p2 c0 {3,S} {6,S} +2 *1 O u0 p2 c0 {3,S} {7,S} +3 *2 C u0 p0 c0 {1,S} {2,S} {4,S} {5,S} +4 H u0 p0 c0 {3,S} +5 H u0 p0 c0 {3,S} +6 H u0 p0 c0 {1,S} +7 *4 X u0 p0 c0 {2,S} + +CH2O* +1 *1 O u0 p2 c0 {2,D} +2 *2 C u0 p0 c0 {1,D} {3,S} {4,S} +3 H u0 p0 c0 {2,S} +4 H u0 p0 c0 {2,S} +5 *4 X u0 p0 c0 + +OH* +1 *3 O u0 p2 c0 {2,S} {3,S} +2 H u0 p0 c0 {1,S} +3 *5 X u0 p0 c0 {1,S} + +CH3O_1* +1 *1 O u0 p2 c0 {2,S} {6,S} +2 *2 C u0 p0 c0 {1,S} {3,S} {4,S} {5,S} +3 *3 H u0 p0 c0 {2,S} +4 H u0 p0 c0 {2,S} +5 H u0 p0 c0 {2,S} +6 *4 X u0 p0 c0 {1,S} + +CH2O_2* +1 *2 O u0 p2 c0 {2,D} +2 *1 C u0 p0 c0 {1,D} {3,S} {4,S} +3 H u0 p0 c0 {2,S} +4 H u0 p0 c0 {2,S} +5 *4 X u0 p0 c0 + +CH2OH* +1 *2 O u0 p2 c0 {2,S} {5,S} +2 *1 C u0 p0 c0 {1,S} {3,S} {4,S} {6,S} +3 H u0 p0 c0 {2,S} +4 H u0 p0 c0 {2,S} +5 *3 H u0 p0 c0 {1,S} +6 *4 X u0 p0 c0 {2,S} + +CH3O_5* +1 *3 O u0 p2 c0 {2,S} {6,S} +2 C u0 p0 c0 {1,S} {3,S} {4,S} {5,S} +3 H u0 p0 c0 {2,S} +4 H u0 p0 c0 {2,S} +5 H u0 p0 c0 {2,S} +6 *5 X u0 p0 c0 {1,S} + +H2COOCH3* +1 *1 O u0 p2 c0 {2,S} {9,S} +2 *2 C u0 p0 c0 {1,S} {3,S} {5,S} {10,S} +3 *3 O u0 p2 c0 {2,S} {4,S} +4 C u0 p0 c0 {3,S} {6,S} {7,S} {8,S} +5 H u0 p0 c0 {2,S} +6 H u0 p0 c0 {4,S} +7 H u0 p0 c0 {4,S} +8 H u0 p0 c0 {4,S} +9 *4 X u0 p0 c0 {1,S} +10 H u0 p0 c0 {2,S} + +HCOOCH3* +1 *1 O u0 p2 c0 {2,D} +2 *2 C u0 p0 c0 {1,D} {3,S} {5,S} +3 O u0 p2 c0 {2,S} {4,S} +4 C u0 p0 c0 {3,S} {6,S} {7,S} {8,S} +5 H u0 p0 c0 {2,S} +6 H u0 p0 c0 {4,S} +7 H u0 p0 c0 {4,S} +8 H u0 p0 c0 {4,S} +9 *4 X u0 p0 c0 + +H2COOCH3_2* +1 *1 O u0 p2 c0 {2,S} {9,S} +2 *2 C u0 p0 c0 {1,S} {3,S} {5,S} {10,S} +3 O u0 p2 c0 {2,S} {4,S} +4 C u0 p0 c0 {3,S} {6,S} {7,S} {8,S} +5 *3 H u0 p0 c0 {2,S} +6 H u0 p0 c0 {4,S} +7 H u0 p0 c0 {4,S} +8 H u0 p0 c0 {4,S} +9 *4 X u0 p0 c0 {1,S} +10 H u0 p0 c0 {2,S} diff --git a/input/kinetics/families/Surface_Dissociation_Beta_vdW/training/reactions.py b/input/kinetics/families/Surface_Dissociation_Beta_vdW/training/reactions.py index 0dcf9b6396..e9fadc4791 100755 --- a/input/kinetics/families/Surface_Dissociation_Beta_vdW/training/reactions.py +++ b/input/kinetics/families/Surface_Dissociation_Beta_vdW/training/reactions.py @@ -7,3 +7,199 @@ Put kinetic parameters for specific reactions in this file to use as a training set for generating rate rules to populate this kinetics family. """ + +# in the reverse direction of family direction +entry( + index = 45, + label = "CO2_2* + H* <=> COOH* + X_5", + degeneracy = 2, + kinetics = SurfaceArrhenius( + A = (6.25E20, 'm^2/(mol*s)'), + n = -0.475, + Ea = (117200, 'J/mol'), + Tmin = (200, 'K'), + Tmax = (3000, 'K'), + ), + rank = 10, + shortDesc = u"""Default""", + longDesc = u"""R45 + test surface mechanism: based upon Olaf Deutschmann's work: + "Surface Reaction Kinetics of Steam- and CO2-Reforming as well as Oxidation of Methane over Nickel-Based Catalysts" + Delgado et al + Catalysts, 2015, 5, 871-904""", + metal = "Ni", +) + +# in the reverse direction of family direction +entry( + index = 17, + label = "CO2* + H* <=> HCOO* + X_5", + degeneracy = 2, + kinetics = SurfaceArrhenius( + A = (1.243e18, 'm^2/(mol*s)'), + n = 0., + Ea = (0.87, 'eV/molecule'), + Tmin = (298, 'K'), + Tmax = (2000, 'K'), + ), + rank = 10, + shortDesc = u"""Default""", + longDesc = u""" +Reaction 17 from table 2 in "Mechanism of Methanol Synthesis on Cu through CO2 +and CO Hydrogenation", Grabow and Mavrikakis. doi:10.1021/cs200055d + +A factor from paper / surface site density of Cu +3.658e13 1/s / 2.943e‐5 mol/m^2 = 1.243e18 m^2/(mol*s) +""", + metal = "Cu", +) + +# in the reverse direction of family direction +entry( + index = 20, + label = "HCOOH* + H* <=> CH3O2_2* + X_5", + degeneracy = 1, + kinetics = SurfaceArrhenius( + A = (2.122e19, 'm^2/(mol*s)'), + n = 0., + Ea = (1.04, 'eV/molecule'), + Tmin = (298, 'K'), + Tmax = (2000, 'K'), + ), + rank = 10, + shortDesc = u"""Default""", + longDesc = u""" +Reaction 20 from table 2 in "Mechanism of Methanol Synthesis on Cu through CO2 +and CO Hydrogenation", Grabow and Mavrikakis. doi:10.1021/cs200055d + +A factor from paper / surface site density of Cu +6.244e14 1/s / 2.943e‐5 mol/m^2 = 2.122e19 m^2/(mol*s) +""", + metal = "Cu", +) + +# in the reverse direction of family direction +entry( + index = 23, + label = "CH2O* + OH* <=> CH3O2* + X_5", + degeneracy = 1, + kinetics = SurfaceArrhenius( + A = (3.401e17, 'm^2/(mol*s)'), + n = 0., + Ea = (0., 'kcal/mol'), + Tmin = (298, 'K'), + Tmax = (2000, 'K'), + ), + rank = 10, + shortDesc = u"""Default""", + longDesc = u""" +Reaction 23 from table 2 in "Mechanism of Methanol Synthesis on Cu through CO2 +and CO Hydrogenation", Grabow and Mavrikakis. doi:10.1021/cs200055d + +Spontaneous in this direction, so 1e13 and barrierless assumed in paper + +A factor from paper / surface site density of Cu +1.001e13 1/s / 2.943e‐5 mol/m^2 = 3.401e17 m^2/(mol*s) +""", + metal = "Cu", +) + +# in the reverse direction of family direction +entry( + index = 24, + label = "CH2O* + H* <=> CH3O_1* + X_5", + degeneracy = 1, + kinetics = SurfaceArrhenius( + A = (6.167e17, 'm^2/(mol*s)'), + n = 0., + Ea = (0.24, 'eV/molecule'), + Tmin = (298, 'K'), + Tmax = (2000, 'K'), + ), + rank = 10, + shortDesc = u"""Default""", + longDesc = u""" +Reaction 24 from table 2 in "Mechanism of Methanol Synthesis on Cu through CO2 +and CO Hydrogenation", Grabow and Mavrikakis. doi:10.1021/cs200055d + +A factor from paper / surface site density of Cu +1.815e13 1/s / 2.943e‐5 mol/m^2 = 6.167e17 m^2/(mol*s) +Erxn = -1.02 eV +""", + metal = "Cu", +) + +# in the reverse direction of family direction +entry( + index = 31, + label = "CH2O_2* + H* <=> CH2OH* + X_5", + degeneracy = 1, + kinetics = SurfaceArrhenius( + A = (3.234e19, 'm^2/(mol*s)'), + n = 0., + Ea = (0.82, 'eV/molecule'), + Tmin = (298, 'K'), + Tmax = (2000, 'K'), + ), + rank = 10, + shortDesc = u"""Default""", + longDesc = u""" +Reaction 31 from table 2 in "Mechanism of Methanol Synthesis on Cu through CO2 +and CO Hydrogenation", Grabow and Mavrikakis. doi:10.1021/cs200055d + +A factor from paper / surface site density of Cu +9.518e14 1/s / 2.943e‐5 mol/m^2 = 3.234e19 m^2/(mol*s) +Erxn = -0.06 eV +""", + metal = "Cu", +) + +# in the reverse direction of family direction +entry( + index = 47, + label = "CH3O_5* + CH2O* <=> H2COOCH3* + X_5", + degeneracy = 1, + kinetics = SurfaceArrhenius( + A = (2.176e18, 'm^2/(mol*s)'), + n = 0., + Ea = (0.13, 'eV/molecule'), + Tmin = (298, 'K'), + Tmax = (2000, 'K'), + ), + rank = 10, + shortDesc = u"""Default""", + longDesc = u""" +Reaction 47 from table 2 in "Mechanism of Methanol Synthesis on Cu through CO2 +and CO Hydrogenation", Grabow and Mavrikakis. doi:10.1021/cs200055d + +A factor from paper / surface site density of Cu +6.405e13 1/s / 2.943e‐5 mol/m^2 = 2.176e18 m^2/(mol*s) +Erxn = -0.78 eV +""", + metal = "Cu", +) + +# in the reverse direction of family direction +entry( + index = 48, + label = "HCOOCH3* + H* <=> H2COOCH3_2* + X_5", + degeneracy = 1, + kinetics = SurfaceArrhenius( + A = (5.219e16, 'm^2/(mol*s)'), + n = 0., + Ea = (0.94, 'eV/molecule'), + Tmin = (298, 'K'), + Tmax = (2000, 'K'), + ), + rank = 10, + shortDesc = u"""Default""", + longDesc = u""" +Reaction 48 from table 2 in "Mechanism of Methanol Synthesis on Cu through CO2 +and CO Hydrogenation", Grabow and Mavrikakis. doi:10.1021/cs200055d + +A factor from paper / surface site density of Cu +1.536e12 1/s / 2.943e‐5 mol/m^2 = 5.219e16 m^2/(mol*s) +Erxn = 0.01 eV +""", + metal = "Cu", +) \ No newline at end of file