# Supplementary Material (ESI) for PCCP # This journal is (c) the Owner Societies 2009 ! rate coefficients obtained from the ME ! Fernandes, R.X., Zádor, J., Jusinski, L.E., Taatjes, C.A., and Miller, J.A., ! Formally direct pathways and low-temperature chain branching in hydrocarbon autoignition: ! The cyclohexyl + O2 reaction at high pressure ! Physical Chemistry Chemical Physics, submitted. ! Knepp, A.M., Meloni, G., Jusinski, L.E., Taatjes, C.A., Cavallotti, C., and Klippenstein, S.J., ! Theory, measurements, and modeling of OH and HO2 formation in the reaction of cyclohexyl radicals with O2. ! Physical Chemistry Chemical Physics, 2007 9 4315-4331. ! notations and units are the same as in the mechanism of ! Silke, E.J., Pitz, W.J., Westbrook, C.K., and Ribaucour, M., ! Detailed chemical kinetic modeling of cyclohexane oxidation. ! Journal of Physical Chemistry A, 2007 111 3761-3775. ! available via ! http://www-cmls.llnl.gov/?url=science_and_technology-combustion-cyclohexane ! starting in r + o2 chxrad + o2 => chxo2j 4.74E+17 -1.8 511 PLOG/ 1 4.74E+17 -1.8 511 / PLOG/ 2 1.92E+16 -1.3 102 / PLOG/ 5 2.51E+15 -1.0 -158 / PLOG/ 10 6.57E+14 -0.8 -333 / PLOG/ 20 2.99E+14 -0.7 -436 / PLOG/ 30 2.23E+14 -0.7 -474 / PLOG/ 40 1.92E+14 -0.7 -493 / PLOG/ 50 1.75E+14 -0.7 -506 / chxrad + o2 => chx1q2j 6.44E-46 17.0 -14736 PLOG/ 1 6.44E-46 17.0 -14736 / PLOG/ 2 4.51E+07 4.4 39291 / PLOG/ 5 1.92E-47 17.6 -14753 / PLOG/ 10 3.13E-22 9.7 -5654 / PLOG/ 20 6.99E-11 6.2 -856 / PLOG/ 30 3.27E-07 5.1 1036 / PLOG/ 40 1.61E-05 4.6 2080 / PLOG/ 50 7.61E-05 4.4 2661 / chxrad + o2 => chx1q3j 1.81E+38 -8.1 15839 PLOG/ 1 1.81E+38 -8.1 15839 / PLOG/ 2 2.20E+28 -5.0 12938 / PLOG/ 5 8.36E-06 5.4 998 / PLOG/ 10 1.15E-12 7.4 -1209 / PLOG/ 20 1.34E-17 8.9 -2798 / PLOG/ 30 1.23E-19 9.5 -3439 / PLOG/ 40 8.40E-21 9.8 -3801 / PLOG/ 50 1.49E-21 10.0 -4028 / chxrad + o2 => chx1q4j 8.15E+48 -10.8 23904 PLOG/ 1 8.15E+48 -10.8 23904 / PLOG/ 2 9.27E+52 -12.0 26082 / PLOG/ 5 4.26E-11 7.4 1707 / PLOG/ 10 3.50E-17 9.2 -402 / PLOG/ 20 2.85E-21 10.4 -1790 / PLOG/ 30 6.03E-23 10.9 -2339 / PLOG/ 40 6.44E-24 11.1 -2654 / PLOG/ 50 9.41E-25 11.3 -2936 / chxrad + o2 => cychexene + ho2 7.26E+44 -9.6 21964 PLOG/ 1 7.26E+44 -9.6 21964 / PLOG/ 2 6.17E+39 -8.0 20583 / PLOG/ 5 7.28E-10 7.0 1993 / PLOG/ 10 3.99E-16 8.9 -148 / PLOG/ 20 1.80E-20 10.1 -1611 / PLOG/ 30 2.53E-22 10.6 -2223 / PLOG/ 40 1.96E-23 11.0 -2588 / PLOG/ 50 3.38E-24 11.2 -2835 / chxrad + o2 => chxyo12 + oh 1.55E+47 -10.7 23370 PLOG/ 1 1.55E+47 -10.7 23370 / PLOG/ 2 2.93E-10 6.8 1969 / PLOG/ 5 1.65E+02 3.2 7478 / PLOG/ 10 7.79E-02 4.2 7014 / PLOG/ 20 2.89E-02 4.3 7830 / PLOG/ 30 4.93E-02 4.2 8570 / PLOG/ 40 5.15E-02 4.2 9060 / PLOG/ 50 3.04E-02 4.3 9352 / chxrad + o2 => hex5enal + oh 1.48E+104 -27.7 49961 PLOG/ 1 1.48E+104 -27.7 49961 / PLOG/ 2 2.78E+127 -35.0 59789 / PLOG/ 5 2.89E+03 3.3 13336 / PLOG/ 10 2.13E-10 7.2 8976 / PLOG/ 20 1.44E-20 10.2 5582 / PLOG/ 30 6.75E-23 10.9 5066 / PLOG/ 40 1.98E-23 11.0 5146 / PLOG/ 50 1.15E-18 9.5 7497 / chxrad + o2 => chxyo14 + oh 1.29E+80 -20.4 40269 PLOG/ 1 1.29E+80 -20.4 40269 / PLOG/ 2 4.14E+80 -20.6 41909 / PLOG/ 5 2.07E+16 -0.7 18714 / PLOG/ 10 2.46E+03 3.2 14823 / PLOG/ 20 2.02E-09 6.9 11026 / PLOG/ 30 6.96E-12 7.6 10705 / PLOG/ 40 1.14E-16 9.0 9049 / PLOG/ 50 5.75E-18 9.4 8802 / ! starting in ro2 (w1) chxo2j => chxrad + o2 7.47E+01 3.9 30349 PLOG/ 1 7.47E+01 3.9 30349 / PLOG/ 2 6.75E+01 3.9 30478 / PLOG/ 5 1.12E+05 2.8 30725 / PLOG/ 10 7.42E+04 2.9 30810 / PLOG/ 20 5.95E+04 2.9 30863 / PLOG/ 30 5.58E+04 3.0 30885 / PLOG/ 40 5.54E+04 3.0 30902 / PLOG/ 50 5.16E+04 3.0 30900 / chxo2j => chx1q2j 1.33E+12 -0.3 28800 PLOG/ 1 1.33E+12 -0.3 28800 / PLOG/ 2 1.89E+01 6.7 58646 / PLOG/ 5 2.02E-05 5.5 28557 / PLOG/ 10 2.35E-10 6.7 23443 / PLOG/ 20 3.55E-06 5.4 24113 / PLOG/ 30 9.53E-06 5.2 23948 / PLOG/ 40 2.25E-05 5.1 23956 / PLOG/ 50 1.12E-04 4.9 24191 / chxo2j => chx1q3j 4.10E+00 3.4 20707 PLOG/ 1 4.10E+00 3.4 20707 / PLOG/ 2 3.11E+00 3.4 20685 / PLOG/ 5 8.60E+03 2.3 22079 / PLOG/ 10 2.34E+03 2.5 21866 / PLOG/ 20 1.07E+03 2.6 21742 / PLOG/ 30 7.03E+02 2.7 21670 / PLOG/ 40 6.25E+02 2.7 21653 / PLOG/ 50 5.66E+02 2.7 21637 / chxo2j => chx1q4j 1.80E+02 2.8 25319 PLOG/ 1 1.80E+02 2.8 25319 / PLOG/ 2 7.59E+01 3.0 25448 / PLOG/ 5 3.07E+05 1.9 26958 / PLOG/ 10 6.15E+04 2.1 26887 / PLOG/ 20 9.91E+03 2.4 26711 / PLOG/ 30 3.15E+03 2.5 26563 / PLOG/ 40 1.46E+03 2.7 26452 / PLOG/ 50 6.06E+02 2.8 26308 / chxo2j => cychexene + ho2 2.40E+02 3.3 26324 PLOG/ 1 2.40E+02 3.3 26324 / PLOG/ 2 1.96E+02 3.3 26377 / PLOG/ 5 7.33E+05 2.2 27522 / PLOG/ 10 3.05E+05 2.3 27480 / PLOG/ 20 1.66E+05 2.4 27431 / PLOG/ 30 1.32E+05 2.4 27407 / PLOG/ 40 1.20E+05 2.5 27403 / PLOG/ 50 1.13E+05 2.5 27397 / chxo2j => chxyo12 + oh 4.72E-01 4.6 33355 PLOG/ 1 4.72E-01 4.6 33355 / PLOG/ 2 2.10E+00 4.8 36376 / PLOG/ 5 2.47E+02 2.8 27587 / PLOG/ 10 1.29E+45 -11.3 35616 / PLOG/ 20 1.11E+16 -1.9 29295 / PLOG/ 30 1.03E+12 -0.5 29325 / PLOG/ 40 1.96E+10 0.1 29562 / PLOG/ 50 1.75E+09 0.5 29776 / chxo2j => hex5enal + oh 3.92E+00 5.3 42459 PLOG/ 1 3.92E+00 5.3 42459 / PLOG/ 2 4.87E+00 5.3 43405 / PLOG/ 5 3.20E+05 2.0 31541 / PLOG/ 10 3.31E+04 2.3 32308 / PLOG/ 20 8.32E+03 2.5 32837 / PLOG/ 30 5.24E+03 2.5 33084 / PLOG/ 40 1.86E+03 2.6 33074 / PLOG/ 50 3.33E+03 2.5 33313 / chxo2j => chxyo14 + oh 4.72E+00 5.4 44517 PLOG/ 1 4.72E+00 5.4 44517 / PLOG/ 2 5.41E+00 5.5 45740 / PLOG/ 5 4.80E+03 2.8 33857 / PLOG/ 10 9.43E+02 3.1 34938 / PLOG/ 20 3.14E+02 3.2 35802 / PLOG/ 30 1.93E+02 3.3 36188 / PLOG/ 40 1.73E+02 3.3 36451 / PLOG/ 50 1.04E+02 3.4 36546 / ! starting in qooh1 (w2) chx1q2j => chxrad + o2 3.21E+08 1.1 28450 PLOG/ 1 3.21E+08 1.1 28450 / PLOG/ 2 3.42E+01 7.0 60471 / PLOG/ 5 6.98E-08 6.4 26952 / PLOG/ 10 1.84E-15 8.3 20073 / PLOG/ 20 1.24E-09 6.3 21495 / PLOG/ 30 4.93E-07 5.5 22505 / PLOG/ 40 2.52E-06 5.3 22874 / PLOG/ 50 5.28E-05 4.9 23581 / chx1q2j => chxo2j 7.95E-01 2.7 7333 PLOG/ 1 7.95E-01 2.7 7333 / PLOG/ 2 5.61E+07 0.4 10524 / PLOG/ 5 6.09E+09 -0.1 11965 / PLOG/ 10 2.11E+09 0.1 12264 / PLOG/ 20 1.83E+09 0.2 12697 / PLOG/ 30 9.02E+08 0.3 12818 / PLOG/ 40 3.95E+08 0.5 12837 / PLOG/ 50 1.81E+08 0.6 12821 / chx1q2j => chx1q3j 1.29E+74 -20.3 44205 PLOG/ 1 1.29E+74 -20.3 44205 / PLOG/ 2 6.86E-02 6.1 44238 / PLOG/ 5 5.41E-24 10.5 13729 / PLOG/ 10 1.12E-17 8.3 14516 / PLOG/ 20 1.14E-16 7.9 14397 / PLOG/ 30 8.60E-15 7.3 15268 / PLOG/ 40 1.60E-12 6.6 16427 / PLOG/ 50 1.59E-11 6.3 17029 / chx1q2j => chx1q4j 2.75E+74 -20.8 44995 PLOG/ 1 2.75E+74 -20.8 44995 / PLOG/ 2 2.58E-02 5.9 44138 / PLOG/ 5 3.49E-14 7.3 19213 / PLOG/ 10 4.02E-18 8.3 16036 / PLOG/ 20 8.82E-13 6.6 18185 / PLOG/ 30 2.11E-11 6.2 18957 / PLOG/ 40 3.94E-10 5.8 19743 / PLOG/ 50 2.42E-08 5.3 20753 / chx1q2j => cychexene + ho2 9.07E+13 -0.8 15495 PLOG/ 1 9.07E+13 -0.8 15495 / PLOG/ 2 1.47E+12 -0.1 15426 / PLOG/ 5 3.26E+19 -2.3 18231 / PLOG/ 10 3.73E+21 -2.8 19580 / PLOG/ 20 1.11E+23 -3.2 20719 / PLOG/ 30 4.04E+23 -3.3 21257 / PLOG/ 40 4.25E+23 -3.3 21480 / PLOG/ 50 3.48E+23 -3.2 21603 / chx1q2j => chxyo12 + oh 1.18E+26 -4.6 15310 PLOG/ 1 1.18E+26 -4.6 15310 / PLOG/ 2 1.30E+24 -3.9 15021 / PLOG/ 5 8.25E+14 -0.9 12116 / PLOG/ 10 1.48E+15 -0.9 12549 / PLOG/ 20 2.43E+15 -0.9 12955 / PLOG/ 30 2.27E+15 -0.9 13113 / PLOG/ 40 1.54E+15 -0.8 13154 / PLOG/ 50 8.61E+14 -0.7 13133 / chx1q2j => hex5enal + oh 4.02E+02 3.3 33548 PLOG/ 1 4.02E+02 3.3 33548 / PLOG/ 2 3.43E+01 8.0 74901 / PLOG/ 5 8.85E-02 5.0 40147 / PLOG/ 10 4.30E-06 5.6 32861 / PLOG/ 20 6.59E-04 4.5 31471 / PLOG/ 30 1.67E-06 5.2 29719 / PLOG/ 40 1.61E-05 4.8 30006 / PLOG/ 50 8.28E-03 3.9 31221 / chx1q2j => chxyo14 + oh 1.94E+05 2.0 31843 PLOG/ 1 1.94E+05 2.0 31843 / PLOG/ 2 3.30E+01 7.4 69944 / PLOG/ 5 6.82E-02 4.8 38762 / PLOG/ 10 7.49E-05 5.1 33413 / PLOG/ 20 7.15E-06 5.2 31289 / PLOG/ 30 1.16E-04 4.7 31489 / PLOG/ 40 1.41E-02 4.0 32396 / PLOG/ 50 2.30E-02 3.9 32568 / ! starting in qooh2 (w3) chx1q3j => chxrad + o2 2.30E+01 5.8 40175 PLOG/ 1 2.30E+01 5.8 40175 / PLOG/ 2 2.45E+01 5.9 41024 / PLOG/ 5 3.98E+05 2.4 26909 / PLOG/ 10 1.96E+01 3.7 25800 / PLOG/ 20 1.33E-03 4.9 24540 / PLOG/ 30 9.64E-04 4.9 24743 / PLOG/ 40 3.08E-04 5.0 24680 / PLOG/ 50 2.38E-04 5.0 24737 / chx1q3j => chxo2j 2.07E-07 5.1 3277 PLOG/ 1 2.07E-07 5.1 3277 / PLOG/ 2 4.97E-09 5.6 2735 / PLOG/ 5 4.68E+05 1.3 8166 / PLOG/ 10 4.96E+04 1.6 7814 / PLOG/ 20 9.88E+03 1.8 7556 / PLOG/ 30 6.89E+03 1.9 7499 / PLOG/ 40 4.63E+03 1.9 7435 / PLOG/ 50 3.56E+03 1.9 7393 / chx1q3j => chx1q2j 2.44E-07 5.7 23585 PLOG/ 1 2.44E-07 5.7 23585 / PLOG/ 2 4.68E+01 7.3 65517 / PLOG/ 5 3.06E-08 6.3 27507 / PLOG/ 10 5.39E-16 8.1 19254 / PLOG/ 20 1.10E-12 6.8 18900 / PLOG/ 30 2.26E-15 7.6 17292 / PLOG/ 40 7.25E-12 6.5 18771 / PLOG/ 50 3.38E-11 6.3 19080 / chx1q3j => chx1q4j 2.39E+37 -8.0 27980 PLOG/ 1 2.39E+37 -8.0 27980 / PLOG/ 2 5.87E+36 -7.7 27908 / PLOG/ 5 3.35E+11 0.1 18392 / PLOG/ 10 1.19E+10 0.5 17888 / PLOG/ 20 1.43E+09 0.8 17564 / PLOG/ 30 4.12E+08 1.0 17357 / PLOG/ 40 2.98E+08 1.0 17308 / PLOG/ 50 2.53E+08 1.1 17286 / chx1q3j => cychexene + ho2 1.84E+01 5.6 38109 PLOG/ 1 1.84E+01 5.6 38109 / PLOG/ 2 9.43E+00 5.7 38756 / PLOG/ 5 4.20E-02 4.2 22122 / PLOG/ 10 6.00E-06 5.4 21179 / PLOG/ 20 8.07E-08 5.9 20908 / PLOG/ 30 9.67E-08 5.8 21204 / PLOG/ 40 2.78E-08 6.0 21108 / PLOG/ 50 3.65E-08 5.9 21263 / chx1q3j => chxyo12 + oh 2.05E+04 2.0 22899 PLOG/ 1 2.05E+04 2.0 22899 / PLOG/ 2 1.13E+03 2.5 23655 / PLOG/ 5 1.44E+20 -3.1 28530 / PLOG/ 10 6.26E+09 0.3 27472 / PLOG/ 20 1.25E+07 1.2 28094 / PLOG/ 30 1.18E+06 1.5 28538 / PLOG/ 40 3.10E+05 1.7 28898 / PLOG/ 50 1.30E+05 1.8 29204 / chx1q3j => hex5enal + oh 2.99E+22 -3.4 22216 PLOG/ 1 2.99E+22 -3.4 22216 / PLOG/ 2 5.35E+19 -2.5 21375 / PLOG/ 5 9.01E+12 -0.4 18893 / PLOG/ 10 9.44E+10 0.3 18181 / PLOG/ 20 1.25E+10 0.5 17882 / PLOG/ 30 3.38E+09 0.7 17670 / PLOG/ 40 2.09E+09 0.8 17594 / PLOG/ 50 2.28E+09 0.8 17616 / chx1q3j => chxyo14 + oh 3.69E+00 5.2 38081 PLOG/ 1 3.69E+00 5.2 38081 / PLOG/ 2 2.47E+00 5.3 39879 / PLOG/ 5 6.00E+04 2.3 30842 / PLOG/ 10 1.81E+03 2.9 32238 / PLOG/ 20 5.39E+01 3.3 33311 / PLOG/ 30 3.23E-01 4.0 33161 / PLOG/ 40 1.69E-01 4.0 33553 / PLOG/ 50 9.51E-03 4.4 33347 / ! starting in qooh3 (w3) chx1q4j => chxrad + o2 5.91E+00 3.9 24857 PLOG/ 1 5.91E+00 3.9 24857 / PLOG/ 2 9.96E+02 3.1 25773 / PLOG/ 5 3.93E+06 2.0 27925 / PLOG/ 10 7.48E+04 2.6 28385 / PLOG/ 20 4.26E+01 3.6 27946 / PLOG/ 30 4.17E-02 4.5 27082 / PLOG/ 40 4.04E-03 4.8 26920 / PLOG/ 50 3.83E-03 4.8 27103 / chx1q4j => chxo2j 5.07E+04 1.7 11315 PLOG/ 1 5.07E+04 1.7 11315 / PLOG/ 2 8.45E+02 2.3 10929 / PLOG/ 5 1.95E+13 -0.9 15292 / PLOG/ 10 9.81E+09 0.2 14125 / PLOG/ 20 2.77E+07 1.0 13198 / PLOG/ 30 1.25E+06 1.4 12691 / PLOG/ 40 3.73E+05 1.6 12499 / PLOG/ 50 1.37E+05 1.7 12335 / chx1q4j => chx1q2j 5.81E+04 1.9 27689 PLOG/ 1 5.81E+04 1.9 27689 / PLOG/ 2 2.41E+01 7.0 63130 / PLOG/ 5 3.73E-09 6.5 28020 / PLOG/ 10 6.31E-11 6.6 23162 / PLOG/ 20 9.73E-10 6.0 22099 / PLOG/ 30 4.22E-11 6.4 21150 / PLOG/ 40 1.92E-11 6.4 20949 / PLOG/ 50 1.91E-09 5.8 21888 / chx1q4j => chx1q3j 1.67E+05 1.8 21367 PLOG/ 1 1.67E+05 1.8 21367 / PLOG/ 2 1.60E+01 3.1 20883 / PLOG/ 5 5.62E+07 1.1 24619 / PLOG/ 10 9.59E+00 3.2 22722 / PLOG/ 20 8.01E-07 5.3 20484 / PLOG/ 30 5.20E-08 5.7 20389 / PLOG/ 40 9.29E-08 5.6 20767 / PLOG/ 50 1.12E-08 5.8 20528 / chx1q4j => cychexene + ho2 1.07E+04 2.5 23410 PLOG/ 1 1.07E+04 2.5 23410 / PLOG/ 2 1.42E+02 3.1 23801 / PLOG/ 5 2.00E+06 1.8 26501 / PLOG/ 10 3.59E+01 3.3 25565 / PLOG/ 20 5.14E-05 5.1 23931 / PLOG/ 30 9.50E-05 5.0 24515 / PLOG/ 40 2.81E-05 5.2 24556 / PLOG/ 50 4.25E-05 5.1 24827 / chx1q4j => chxyo12 + oh 4.22E+04 1.8 23681 PLOG/ 1 4.22E+04 1.8 23681 / PLOG/ 2 2.13E+03 2.3 24675 / PLOG/ 5 2.00E+15 -1.6 28325 / PLOG/ 10 2.94E+08 0.7 28320 / PLOG/ 20 1.01E+06 1.6 29193 / PLOG/ 30 1.15E+05 1.9 29784 / PLOG/ 40 3.32E+04 2.1 30243 / PLOG/ 50 1.42E+04 2.2 30605 / chx1q4j => hex5enal + oh 2.33E+00 5.2 37965 PLOG/ 1 2.33E+00 5.2 37965 / PLOG/ 2 3.71E+00 5.2 39964 / PLOG/ 5 3.40E+04 2.4 30979 / PLOG/ 10 1.21E+03 2.9 32391 / PLOG/ 20 1.55E+01 3.5 33304 / PLOG/ 30 6.14E-02 4.2 33084 / PLOG/ 40 1.89E-01 4.0 33822 / PLOG/ 50 1.60E-01 4.0 34155 / chx1q4j => chxyo14 + oh 8.35E+29 -5.5 24241 PLOG/ 1 8.35E+29 -5.5 24241 / PLOG/ 2 5.11E+27 -4.8 23791 / PLOG/ 5 2.08E+23 -3.4 22453 / PLOG/ 10 7.25E+19 -2.3 21268 / PLOG/ 20 1.31E+17 -1.4 20293 / PLOG/ 30 8.19E+15 -1.0 19857 / PLOG/ 40 1.53E+15 -0.8 19590 / PLOG/ 50 5.47E+14 -0.7 19426 /