From 65aa1b0fe9bc9a06ce41b815779541eaf8002be7 Mon Sep 17 00:00:00 2001 From: alongd Date: Tue, 17 Oct 2017 15:02:49 -0400 Subject: [PATCH] Added the C2H4+O_Klipp2017 kinetic library The reaction of atomic oxygen with ethylene is a fundamental oxidation step in combustion. Since it involves an intersystem crossing from a triplet surface to a singlet surface it requires special treatment. Data taken from http://dx.doi.org/10.1016/j.proci.2016.06.053 --- .../libraries/C2H4+O_Klipp2017/dictionary.txt | 104 ++++++++++++++++++ .../libraries/C2H4+O_Klipp2017/reactions.py | 98 +++++++++++++++++ 2 files changed, 202 insertions(+) create mode 100644 input/kinetics/libraries/C2H4+O_Klipp2017/dictionary.txt create mode 100644 input/kinetics/libraries/C2H4+O_Klipp2017/reactions.py diff --git a/input/kinetics/libraries/C2H4+O_Klipp2017/dictionary.txt b/input/kinetics/libraries/C2H4+O_Klipp2017/dictionary.txt new file mode 100644 index 0000000000..2b03fd070f --- /dev/null +++ b/input/kinetics/libraries/C2H4+O_Klipp2017/dictionary.txt @@ -0,0 +1,104 @@ +C2H4 +1 C u0 p0 c0 {2,D} {3,S} {4,S} +2 C u0 p0 c0 {1,D} {5,S} {6,S} +3 H u0 p0 c0 {1,S} +4 H u0 p0 c0 {1,S} +5 H u0 p0 c0 {2,S} +6 H u0 p0 c0 {2,S} + +O +multiplicity 3 +1 O u2 p2 c0 + +CH3 +multiplicity 2 +1 C u1 p0 c0 {2,S} {3,S} {4,S} +2 H u0 p0 c0 {1,S} +3 H u0 p0 c0 {1,S} +4 H u0 p0 c0 {1,S} + +HCO +multiplicity 2 +1 C u1 p0 c0 {2,S} {3,D} +2 H u0 p0 c0 {1,S} +3 O u0 p2 c0 {1,D} + +CH3CO +multiplicity 2 +1 C u0 p0 c0 {2,S} {4,S} {5,S} {6,S} +2 C u1 p0 c0 {1,S} {3,D} +3 O u0 p2 c0 {2,D} +4 H u0 p0 c0 {1,S} +5 H u0 p0 c0 {1,S} +6 H u0 p0 c0 {1,S} + +H +multiplicity 2 +1 H u1 p0 c0 + +CH2CHO +multiplicity 2 +1 C u1 p0 c0 {2,S} {3,S} {4,S} +2 H u0 p0 c0 {1,S} +3 H u0 p0 c0 {1,S} +4 C u0 p0 c0 {1,S} {5,D} {6,S} +5 O u0 p2 c0 {4,D} +6 H u0 p0 c0 {4,S} + +C2H3 +multiplicity 2 +1 C u1 p0 c0 {2,S} {3,D} +2 H u0 p0 c0 {1,S} +3 C u0 p0 c0 {1,D} {4,S} {5,S} +4 H u0 p0 c0 {3,S} +5 H u0 p0 c0 {3,S} + +OH +multiplicity 2 +1 O u1 p2 c0 {2,S} +2 H u0 p0 c0 {1,S} + +CH2 +multiplicity 3 +1 C u2 p0 c0 {2,S} {3,S} +2 H u0 p0 c0 {1,S} +3 H u0 p0 c0 {1,S} + +CH2O +1 C u0 p0 c0 {2,D} {3,S} {4,S} +2 O u0 p2 c0 {1,D} +3 H u0 p0 c0 {1,S} +4 H u0 p0 c0 {1,S} + +CH2CO +1 C u0 p0 c0 {2,D} {4,S} {5,S} +2 C u0 p0 c0 {1,D} {3,D} +3 O u0 p2 c0 {2,D} +4 H u0 p0 c0 {1,S} +5 H u0 p0 c0 {1,S} + +H2 +1 H u0 p0 c0 {2,S} +2 H u0 p0 c0 {1,S} + +CH4 +1 C u0 p0 c0 {2,S} {3,S} {4,S} {5,S} +2 H u0 p0 c0 {1,S} +3 H u0 p0 c0 {1,S} +4 H u0 p0 c0 {1,S} +5 H u0 p0 c0 {1,S} + +CO +1 C u0 p1 c-1 {2,T} +2 O u0 p1 c+1 {1,T} + +C2H2 +1 C u0 p0 c0 {2,T} {3,S} +2 C u0 p0 c0 {1,T} {4,S} +3 H u0 p0 c0 {1,S} +4 H u0 p0 c0 {2,S} + +H2O +1 O u0 p2 c0 {2,S} {3,S} +2 H u0 p0 c0 {1,S} +3 H u0 p0 c0 {1,S} diff --git a/input/kinetics/libraries/C2H4+O_Klipp2017/reactions.py b/input/kinetics/libraries/C2H4+O_Klipp2017/reactions.py new file mode 100644 index 0000000000..662581defc --- /dev/null +++ b/input/kinetics/libraries/C2H4+O_Klipp2017/reactions.py @@ -0,0 +1,98 @@ +#!/usr/bin/env python +# encoding: utf-8 + +name = "C2H4+O_Klipp2017" +shortDesc = u"C2H4 + O surface with product branching" +longDesc = u""" +The reaction of atomic oxygen with ethylene is a fundamental oxidation step in combustion. + +Decomposition of the initial adduct via spin-allowed reaction channels on the triplet surface competes +with intersystem crossing (ISC) and a set of spin-forbidden reaction channels on the ground-state singlet +surface. This library describes product branching ratios based on the following publication: + +X. Li, A.W. Jasper, J. Zádor, J.A. Miller, S.J. Klippenstein, +Theoretical kinetics of O + C2H4, +Proceedings of the Combustion Institute 36 (2017) 219–227 +http://dx.doi.org/10.1016/j.proci.2016.06.053 + +Several different methods were used: +CCSDT(Q)/cc-pVDZ//CCSD(T)/cc-pVTZ +For barrierless reactions on the spin allowed surface CASPT2(2e,2o)/cc-pVTZ was used. +For reaction with barriers on the spin allowed surface CCSD(T)/CBS//B2PLYPD3/cc-pVTZ was used. +The total ISC rate was calculated using Landau–Zener statistical theory +non-statistical “prompt” branching in the dynamics immediately following ISC was predicted using +direct classical trajectories and the CASPT2(2e,2o)/cc-pVDZ surface. + +Pressure dependence in the product branching fractions and the potential formation of stabilized products were +considered, but results show that rates are pressure-independent (with < 10% variations in the branching fractions) +up to 20 bar at 300 K and up to 200 bar at 1000 K. + +Channels which account for less than 1% of the products are given in this library a low rate: 1e7 cm^3/(mol*s) +(reactions 1a, 1b, 1c, 1e, 1f are all in the 1e10-1e13 cm^3/(mol*s) range at the 300-2500 K range) + +Library written by alongd +""" + +entry( + index = 1, + label = "C2H4 + O <=> CH3 + HCO", + degeneracy = 1, + kinetics = Arrhenius(A=(3.319e+13,'cm^3/(mol*s)'), n=-1.717, Ea=(2893,'cal/mol'), T0=(298,'K'), Tmin=(300,'K'), Tmax=(2500,'K')), + longDesc = u"""Reaction 1a""", +) + +entry( + index = 2, + label = "C2H4 + O <=> CH3CO + H", + degeneracy = 1, + kinetics = Arrhenius(A=(5.485e+11,'cm^3/(mol*s)'), n=-0.4843, Ea=(1958,'cal/mol'), T0=(298,'K'), Tmin=(300,'K'), Tmax=(2500,'K')), + longDesc = u"""Reaction 1b""", +) + +entry( + index = 3, + label = "C2H4 + O <=> CH2CHO + H", + degeneracy = 1, + kinetics = Arrhenius(A=(2.022e+12,'cm^3/(mol*s)'), n=0.9475, Ea=(1724,'cal/mol'), T0=(298,'K'), Tmin=(300,'K'), Tmax=(2500,'K')), + longDesc = u"""Reaction 1c""", +) + +entry( + index = 4, + label = "C2H4 + O <=> C2H3 + OH", + degeneracy = 1, + kinetics = Arrhenius(A=(1e+7,'cm^3/(mol*s)'), n=0, Ea=(0,'cal/mol'), T0=(298,'K'), Tmin=(300,'K'), Tmax=(2500,'K')), + longDesc = u"""Reaction 1d""", +) + +entry( + index = 5, + label = "C2H4 + O <=> CH2 + CH2O", + degeneracy = 1, + kinetics = Arrhenius(A=(4.868e+11,'cm^3/(mol*s)'), n=1.991, Ea=(2860,'cal/mol'), T0=(298,'K'), Tmin=(300,'K'), Tmax=(2500,'K')), + longDesc = u"""Reaction 1e""", +) + +entry( + index = 6, + label = "C2H4 + O <=> CH2CO + H2", + degeneracy = 1, + kinetics = Arrhenius(A=(3.315e+12,'cm^3/(mol*s)'), n=-1.831, Ea=(3180,'cal/mol'), T0=(298,'K'), Tmin=(300,'K'), Tmax=(2500,'K')), + longDesc = u"""Reaction 1f""", +) + +entry( + index = 7, + label = "C2H4 + O <=> CH4 + CO", + degeneracy = 1, + kinetics = Arrhenius(A=(1e+7,'cm^3/(mol*s)'), n=0, Ea=(0,'cal/mol'), T0=(298,'K'), Tmin=(300,'K'), Tmax=(2500,'K')), + longDesc = u"""Reaction 1g""", +) + +entry( + index = 8, + label = "C2H4 + O <=> C2H2 + H2O", + degeneracy = 1, + kinetics = Arrhenius(A=(1e+7,'cm^3/(mol*s)'), n=0, Ea=(0,'cal/mol'), T0=(298,'K'), Tmin=(300,'K'), Tmax=(2500,'K')), + longDesc = u"""Reaction 1h""", +)