#!/usr/bin/env python
# encoding: utf-8

name = "Birad_recombination/training"
shortDesc = u"Reaction kinetics used to generate rate rules"
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.
"""
entry(
    index = 0,
    label = "C8H12 <=> C8H12-2",
    degeneracy = 1.0,
    kinetics = Arrhenius(A=(2e+12,'s^-1'), n=0, Ea=(7.5312,'kJ/mol'), T0=(1,'K'), Tmin=(550,'K'), Tmax=(650,'K')),
    rank = 10,
    shortDesc = """[186] Benson et al.""",
    longDesc = 
"""
[186] Benson, S.W. J. Chem. Phys. 1967, 46, 4920.

CH2=CHCH(.)CH2CH2CH(.)CH=CH2 --> 4-vinylcyclohexene. (Rxn. -c); arises from birad recombination of resonance isomer: .CH2CH=CHCH2CH2CH(.)CH=CH2

Data are estimated.

***this only considers cis-cis isomer reaction*** cis-trans A prefactor is 50% of the value used here; also, on p. 4923, it is stated that cis trans rate is 5/6 of the overall rate, so maybe the k that should be used is 0.6 of the value currently in place?
Verified by Greg Magoon: Rxn. -d. also looks to be of interest here; whether the rate is high-pressure limit was not investigated, but p. 4922 says that pressures involved were low; DE0 uncertainty added; regarding temperature range, I considered dropping lower temperature limit from 550 K to 400 K (based on p. 4923), but it seems that experiments were performed at or around 600 K, so I will leave it at 550-650 K

Note: after some preliminary confusion on my part, it looks like the existing groups are correct (the correct resonance form for the CH2 radical is taken into account with the Ypri_rad_out (i.e. Cpri_rad_out_H2)), but arguably, another, a more-specific group (C_rad_out_H2/OneDe and Cpri_rad_out_H2/OneDe) should be specified to account for delocalizing group at this site

Converted to training reaction from rate rule: R6_SSSDS;C_rad_out_H/OneDe;Cpri_rad_out_2H
""",
)

entry(
    index = 1,
    label = "C4H8 <=> C4H8-2",
    degeneracy = 1.0,
    kinetics = Arrhenius(A=(1.62e+12,'s^-1'), n=-0.305, Ea=(8.28432,'kJ/mol'), T0=(1,'K'), Tmin=(600,'K'), Tmax=(2000,'K')),
    rank = 6,
    shortDesc = """[x] Sirjean et al.""",
    longDesc = 
"""
[x] Sirjean, B.; Glaude, P. A.; Ruiz-Lopez, M. F.; Fournet, R.; J. Phys. Chem. A. 2006, 110, 12693-12704. 
http://dx.doi.org/10.1021/jp0651081
.CH2CH2CH2CH2CH2. -> cyclopentane (k4-1 in Scheme 5/Table 7)

TST calculation

Added by Greg Magoon: Stated pressure is 1 atm, but I believe they are actually calculating the high-pressure limit rate constant

Converted to training reaction from rate rule: R4_SSS;C_rad_out_2H;Cpri_rad_out_2H
""",
)

entry(
    index = 2,
    label = "C5H10 <=> C5H10-2",
    degeneracy = 1.0,
    kinetics = Arrhenius(A=(7.76e+09,'s^-1'), n=0.311, Ea=(7.1128,'kJ/mol'), T0=(1,'K'), Tmin=(600,'K'), Tmax=(2000,'K')),
    rank = 6,
    shortDesc = """[x] Sirjean et al.""",
    longDesc = 
"""
[x] Sirjean, B.; Glaude, P. A.; Ruiz-Lopez, M. F.; Fournet, R.; J. Phys. Chem. A. 2006, 110, 12693-12704. 
http://dx.doi.org/10.1021/jp0651081
.CH2CH2CH2CH2CH2CH2. -> cyclohexane (k5-1+k5-2 in Scheme 7/Table 10) (includes formation of both boat and chair conformations)

TST calculation

Added by Greg Magoon: Stated pressure is 1 atm, but I believe they are actually calculating the high-pressure limit rate constant; the rate constant added here was found my performing least squares fit for log(ktot) from 600-2000 K (where ktot is the sum of k5-1 and k5-2)

Note: Recent experimental/RRKM study by Kiefer, Gupte, Harding, and Klippenstein (http://www.combustion.org.uk/ECM_2009/P810069.pdf) (stated uncertainty is +/- 30%) appears to agree with Sirjean et al. results, but they only report forward rate constant

Converted to training reaction from rate rule: R5_SSSS;C_rad_out_2H;Cpri_rad_out_2H
""",
)

entry(
    index = 3,
    label = "C6H12 <=> C6H12-2",
    degeneracy = 1.0,
    kinetics = Arrhenius(A=(3.21e+10,'s^-1'), n=0.137, Ea=(8.87008,'kJ/mol'), T0=(1,'K'), Tmin=(600,'K'), Tmax=(2000,'K')),
    rank = 6,
    shortDesc = """[x] Sirjean et al.""",
    longDesc = 
"""
Converted to training reaction from rate rule: R6_SSSSS;C_rad_out_2H;Cpri_rad_out_2H
""",
)

entry(
    index = 4,
    label = "CH2S2 <=> CH2S2-2",
    degeneracy = 1.0,
    kinetics = Arrhenius(A=(2.18e+16,'s^-1'), n=0, Ea=(2.9288,'kJ/mol'), T0=(1,'K'), Tmin=(300,'K'), Tmax=(1500,'K')),
    rank = 10,
    shortDesc = """A.G. Vandeputte""",
    longDesc = 
"""
Converted to training reaction from rate rule: R3_SS;S_rad;Spri_rad
""",
)

entry(
    index = 5,
    label = "C8H12 <=> C8H12-2",
    degeneracy = 1.0,
    kinetics = Arrhenius(
        A = (3.49424e+11, 's^-1'),
        n = -0.0806221,
        Ea = (12.5388, 'kJ/mol'),
        T0 = (1, 'K')),
    rank = 5,
    shortDesc = u"""Level of theory: CBS-QB3 with 1D rotors in B3LYP/CBSB7""",
    longDesc = 
u"""
library value for butadiene dimerization reactions calculated by Duminda Ranasinghe and Hao-Wei Pang in March 2019
""",
)

entry(
    index = 6,
    label = "C8H12_DVT <=> C8H12_COD",
    degeneracy = 1,
     kinetics = Arrhenius(
        A = (1.56665e+11, 's^-1'),
        n = -0.0961041,
        Ea = (25.7391, 'kJ/mol'),
        T0 = (1, 'K')),
    rank = 5,
    shortDesc = u"""Level of theory: CBS-QB3 with 1D rotors in B3LYP/CBSB7""",
    longDesc = 
u"""
library value for butadiene dimerization reactions calculated by Duminda Ranasinghe and Hao-Wei Pang in March 2019
""",
)

entry(
    index = 7,
    label = "C8H12_DVT2 <=> C8H12_DVCB",
    degeneracy = 1,
    kinetics = Arrhenius(
        A = (1.3971e+12, 's^-1'),
        n = -0.104026,
        Ea = (16.1686, 'kJ/mol'),
        T0 = (1, 'K')
    ),
    rank = 5,
    shortDesc = u"""Level of theory: CBS-QB3 with 1D rotors in B3LYP/CBSB7""",
    longDesc = 
u"""
library value for butadiene dimerization reactions calculated by Duminda Ranasinghe and Hao-Wei Pang in March 2019
""",
)

