From 275b2ceffa7ab0198e1c1a97137a8fb7bbae577c Mon Sep 17 00:00:00 2001 From: davidfarinajr Date: Mon, 17 Jan 2022 15:37:19 -0500 Subject: [PATCH] added `Singlet_Carbene_Intra_Disproportionation` training reactions --- .../training/dictionary.txt | 72 +++++++++++++++++++ .../training/reactions.py | 66 +++++++++++++++++ 2 files changed, 138 insertions(+) diff --git a/input/kinetics/families/Singlet_Carbene_Intra_Disproportionation/training/dictionary.txt b/input/kinetics/families/Singlet_Carbene_Intra_Disproportionation/training/dictionary.txt index a0120f0311..3ed44fff6d 100644 --- a/input/kinetics/families/Singlet_Carbene_Intra_Disproportionation/training/dictionary.txt +++ b/input/kinetics/families/Singlet_Carbene_Intra_Disproportionation/training/dictionary.txt @@ -110,3 +110,75 @@ C6H6-8 11 *3 H u0 p0 c0 {4,S} 12 H u0 p0 c0 {5,S} +C2F4 +1 *3 F u0 p3 c0 {5,S} +2 F u0 p3 c0 {5,S} +3 F u0 p3 c0 {5,S} +4 F u0 p3 c0 {6,S} +5 *2 C u0 p0 c0 {1,S} {2,S} {3,S} {6,S} +6 *1 C u0 p1 c0 {4,S} {5,S} + +C2F4-2 +1 *3 F u0 p3 c0 {6,S} +2 F u0 p3 c0 {5,S} +3 F u0 p3 c0 {5,S} +4 F u0 p3 c0 {6,S} +5 *2 C u0 p0 c0 {2,S} {3,S} {6,D} +6 *1 C u0 p0 c0 {1,S} {4,S} {5,D} + +CH3CCl +1 *3 H u0 p0 c0 {5,S} +2 H u0 p0 c0 {5,S} +3 H u0 p0 c0 {5,S} +4 Cl u0 p3 c0 {6,S} +5 *2 C u0 p0 c0 {1,S} {2,S} {3,S} {6,S} +6 *1 C u0 p1 c0 {4,S} {5,S} + +CH2CHCl +1 *3 H u0 p0 c0 {6,S} +2 H u0 p0 c0 {5,S} +3 H u0 p0 c0 {5,S} +4 Cl u0 p3 c0 {6,S} +5 *2 C u0 p0 c0 {2,S} {3,S} {6,D} +6 *1 C u0 p0 c0 {1,S} {4,S} {5,D} + +CH3CF +1 *3 H u0 p0 c0 {5,S} +2 H u0 p0 c0 {5,S} +3 H u0 p0 c0 {5,S} +4 F u0 p3 c0 {6,S} +5 *2 C u0 p0 c0 {1,S} {2,S} {3,S} {6,S} +6 *1 C u0 p1 c0 {4,S} {5,S} + +CH2CHF +1 *3 H u0 p0 c0 {6,S} +2 H u0 p0 c0 {5,S} +3 H u0 p0 c0 {5,S} +4 F u0 p3 c0 {6,S} +5 *2 C u0 p0 c0 {2,S} {3,S} {6,D} +6 *1 C u0 p0 c0 {1,S} {4,S} {5,D} + +CH3CH2CBr +1 C u0 p0 c0 {2,S} {5,S} {6,S} {7,S} +2 *2 C u0 p0 c0 {1,S} {3,S} {8,S} {9,S} +3 *1 C u0 p1 c0 {2,S} {4,S} +4 Br u0 p3 c0 {3,S} +5 H u0 p0 c0 {1,S} +6 H u0 p0 c0 {1,S} +7 H u0 p0 c0 {1,S} +8 *3 H u0 p0 c0 {2,S} +9 H u0 p0 c0 {2,S} + +CH3CHCHBr +1 C u0 p0 c0 {2,S} {5,S} {6,S} {7,S} +2 *2 C u0 p0 c0 {1,S} {3,D} {8,S} +3 *1 C u0 p0 c0 {2,D} {4,S} {9,S} +4 Br u0 p3 c0 {3,S} +5 H u0 p0 c0 {1,S} +6 H u0 p0 c0 {1,S} +7 H u0 p0 c0 {1,S} +8 H u0 p0 c0 {2,S} +9 *3 H u0 p0 c0 {3,S} + + + diff --git a/input/kinetics/families/Singlet_Carbene_Intra_Disproportionation/training/reactions.py b/input/kinetics/families/Singlet_Carbene_Intra_Disproportionation/training/reactions.py index 2b8dff0ff5..3bd2c8f8fa 100644 --- a/input/kinetics/families/Singlet_Carbene_Intra_Disproportionation/training/reactions.py +++ b/input/kinetics/families/Singlet_Carbene_Intra_Disproportionation/training/reactions.py @@ -6,6 +6,16 @@ longDesc = u""" Put kinetic parameters for specific reactions in this file to use as a training set for generating rate rules to populate this kinetics family. +Sources: +[1] Characterization of the 1,1-HCl Elimination Reaction of Vibrationally Excited CD3CHFCl Molecules and Assignment of Threshold Energies for 1,1-HCl and 1,2-DCl plus 1,1-HF and 1,2-DF Elimination Reactions + Timothy M. Brown, Matthew J. Nestler, Samuel M. Rossabi, George L. Heard, D. W. Setser, and Bert E. Holmes + The Journal of Physical Chemistry A 2015 119 (36), 9441-9451 + DOI: 10.1021/acs.jpca.5b06638 + +[2] Unimolecular HBr and HF Elimination Reactions of Vibrationally Excited C2H5CH2Br and C2D5CHFBr: Identification of the 1,1-HBr Elimination Reaction from C2D5CHFBr and Search for the C2D5(F)C:HBr Adduct + Timothy M. Brown, Blanton R. Gillespie, Mallory M. Rothrock, Anthony J. Ranieri, Melinda K. Schueneman, George L. Heard, Donald W. Setser, and Bert E. Holmes + The Journal of Physical Chemistry A 2019 123 (41), 8776-8786 + DOI: 10.1021/acs.jpca.9b07029 """ entry( index = 0, @@ -59,3 +69,59 @@ """, ) +entry( + index = 4, + label = "C2F4 <=> C2F4-2", + degeneracy = 3.0, + kinetics = Arrhenius(A=(5.731e+10,'s^-1'), n=0.827, Ea=(35644,'cal/mol'), T0=(1,'K')), + rank = 10, + shortDesc = """The chemkin file reaction is CF3CF <=> CF2:CF2""", + longDesc = +""" +Training reaction from kinetics library: YF +Original entry: CF3CF <=> CF2:CF2 +""", +) + +entry( + index = 5, + label = "CH3CF <=> CH2CHF", + degeneracy = 3.0, + kinetics = Arrhenius(A=(1e13,'s^-1'), n=0, Ea=(15,'kcal/mol'), T0=(1,'K')), + rank = 10, + shortDesc = """MP2/6-311+G(2d,p)""", + longDesc = +""" +Ea is threshold energy for CD3CF -> CD2=CDF from Figure 1 in [1] +A factor estimated +""", +) + +entry( + index = 6, + label = "CH3CCl <=> CH2CHCl", + degeneracy = 3.0, + kinetics = Arrhenius(A=(1e13,'s^-1'), n=0, Ea=(10,'kcal/mol'), T0=(1,'K')), + rank = 10, + shortDesc = """MP2/6-311+G(2d,p)""", + longDesc = +""" +Ea is threshold energy for CD3CCl -> CD2=CDCl from Figure 1 in [1] +A factor estimated +""", +) + +entry( + index = 7, + label = "CH3CH2CBr <=> CH3CHCHBr", + degeneracy = 2.0, + kinetics = Arrhenius(A=(1e13,'s^-1'), n=0, Ea=(4.2,'kcal/mol'), T0=(1,'K')), + rank = 10, + shortDesc = """MP2/6-311+G(2d,p)""", + longDesc = +""" +Ea is threshold energy for CD3CD2CCl -> CD3CD=CDCl from Figure 6 in [2] +A factor estimated +""", +) +