Species Fraction Time (sec) Average Vibrational Energy (cm ) Multiwell Solves time-dependent 1-D energy transfer master equations Solved stochastically using the Gillespie algorithm -Argon was the bath gas collider average vibrational energy of reactant k T,P = slope k T,P
Temperature dependent E down expression from Hippler, Troe, Wendelken, JCP E down E down = 260 cm -1 E down = cm -1 Lin and Lin (1986)
Correlation with Aromaticity Harmonic Oscillator Measure of Aromaticity HOMA = 1 (aromatic form of benzene) HOMA = 0 (Kekulè form of benzene) HOMA = HOMA limiting values
kcal/mol Energy Correlation with Aromaticity Zubarev, Robertson, Domin, McClean, Wang, Lester, Whitesides, You, Frenklach, JPC C 2010
Zigzag vs Armchair Armchair I Armchair II Zigzag I Zigzag II 1 atm ZZ I ZZ II AC II AC I ZZ I ZZ II AC II AC I
HOMA HOMA oxyradical ring Barrier height (kcal/mol) k T = 2000 K, P = (s -1 ) Kinetics Correlation with HOMA?
Conclusions The decomposition of oxyradicals: temperature, pressure, substrate-size, site dependent armchair rates are close to those of a zigzag-edge correlated with aromaticity The following generalization can be made: 2 free edges free edge 1 free edge free edge no free edges > >> Proliferation of zigzag-edges in flames
DOE-BES Prof. William A. Lester, Jr. Dr. Dmitry Zubarev (moving to Harvard U.) Dr. Russell Whitesides (now at LLNL) Prof. Xiaoqing You (now at Tsinghua U.) David Edwards