First-principles chemistry for combustion of hydrocarbon fuels

In the area of the chemical kinetics, there are several challenges in building complete kinetic mechanisms that are essential in understanding hydrocarbon oxidation processes, especially combustion of hydrocarbon fuels. The two main challenges in building such mechanisms are: (i) how to estimate kinetic parameters for numerous elementary reactions quickly and reliably and (ii) how to calculate overall thermal and pressure-dependent rate constants for complicated processes taking place on multiple, interconnected potential wells. The first part of this dissertation presents the further development of the Reaction Class---Transition State Theory (RC-TST) in estimating reliable rate constants of elementary reactions in a reaction class. The applications of this methodology are presented for the four hydrogen abstraction reaction classes: (i) OH + Alkane → H2O + Alkyl, (ii) O(3P)+ Alkane → OH + Alkyl, (iii) CHO + Alkane → HCHO + Alkyl, and (iv) H + Alkene → H2 + Alkenyl. The second part shows the implementation of the Master Equation (ME) approach in calculating the overall rate constants for complex processes, particularly for the reaction of OH radical with propene on the potential energy surface of 8 intermediates, 22 transition states and 8 products channels. With a successful demonstration of the applications of the two kinetic tools, confidence has been gained in building such complete kinetic mechanisms for combustion of hydrocarbon fuels.; Chapter 1 is an overview on the main challenges in building complete kinetic mechanisms for combustion of hydrocarbon fuels. The suggested solutions to address these challenges are also introduced in this chapter. Chapter 2 presents the RC-TST methodology. Several applications of the RC-TST are presented in Chapter 3. Chapter 4 is about the implementation of the ME methodology in calculating the pressure-dependent rate constants for complex reactions on multiple, interconnected potential energy surface. An illustration is given as "Kinetics of Enol Formation from Reaction of OH with Propene."...