Reaction mechanisms in aromatic hydrocarbon formation involving the C5H5 cyclopentadienyl moiety

Detailed chemical kinetic models for the low-temperature combustion of hydrocarbons with application to gasoline and diesel fuel surrogates

“…Lifshitz et al [305] have studied the thermal reaction of methylcyclopentadiene, including the formation of benzene, which takes place only from radical intermediates that have a methylene group connected to the five-membered ring. Melius et al [306] have calculated the potential energy surface for the formation of naphthalene from two cyclopentadienyl radicals and have proposed that it occurs in two steps: the formation of H-atoms and dihydrofulvalenyl (•C 10 H 9 ) radicals followed by the decomposition of these radicals to give naphthalene and H-atoms. While this channel has been proven to be important under flame conditions [307], the formation of dihydrofulvalene (C 10 H 10 , see figure 29c) should be also envisaged at low temperature [256,308].…”

Computed Rate Coefficients and Product Yields for c-C5H5 + CH3 → Products

“…The reduced moment of inertia based on the equilibrium geometry was calculated using the formulas described by Pitzer. [24][25][26] In this paper we have used the reduced moment of inertia I (2,3) , 27 and the one dimensional Schroedinger equation was solved numerically. For cyclopentadienyl an additional moment of inertia for pseudo rotation was used as described in Section 3.1.…”

“…The predicted thermochemical properties for all the molecules included in this study are tabulated in Table 5. Also the thermochemical values calculated by Melius et al 2 using the BAC-MP4 method are compared to the ones calculated here using the CBS-QB3 method in Table 6.…”

“…In literature many pathways have been mentioned which lead to benzene formation from C 6 H 7 . 2,52 In some practical situations these C 6 H 7 molecules are formed predominantly by the pathways in Figure 1. At most temperatures and pressures the formation of R2 is about an order of magnitude greater than the the second fastest forming product R1+H (see Figure 14).…”

“…1 Although the potential energy surface was computed in the 1990's by Melius et al 2 and Moskaleva et al 3 more precise calculations are now possible. Even with an accurate PES the calculation of the pressure dependent gas-phase rate coefficients is a challenging task.…”