Alkylperoxyl (RO2) and hydroperoxyalkyl (QOOH) species are crucial intermediates produced during the autoignition of transport fuels, consequently their thermodynamic kinetic data very important. Since these not available experimentally, we take up challenge computing them from first principles. We compare 1,5 shifts in 2-methyl-4-heptylperoxyl radical 3-methylcyclohexylperoxy to clarify simila...

Rate coefficients for the reactions of C2H radicals with methane (k1), ethane (k2), propane (k3), ethylene (k4), and propylene (k5) were computed using canonical variational transition state theory (CVT) coupled with hybrid-meta density functional theory (DFT) over a wide range of temperatures from 150 to 5000 K. The quantum chemical tunneling effect was corrected by the small curvature tunneli...

This work presents a detailed kinetic modelling study of the thermal pyrolysis of tetraethoxysilane (TEOS). A chemical mechanism is proposed based on an analogy between the hydrocarbon branches attached to the central silicon atom and an existing mechanism for the decomposition and combustion of ethanol. Important reaction pathways are identified through element flux and sensitivity analyses. I...

A method for incorporating quantum mechanics into enzyme kinetics modeling is presented. Three aspects are emphasized: 1) combined quantum mechanical and molecular mechanical methods are used to represent the potential energy surface for modeling bond forming and breaking processes, 2) instantaneous normal mode analyses are used to incorporate quantum vibrational free energies to the classical ...

The hydrogen abstraction reaction of the OH radical with CH(2)FCH(2)F (HFC-152) is studied theoretically over the 150-3000 K temperature range. In this study, the two most recently developed hybrid density functional theories, namely, BB1K and MPWB1K, are applied, and their efficiency in reaction dynamics calculation is discussed. The BB1K/6-31+G(d,p) method gives the best result for the potent...

CONSPECTUS: The active site of an enzyme is surrounded by a fluctuating environment of protein and solvent conformational states, and a realistic calculation of chemical reaction rates and kinetic isotope effects of enzyme-catalyzed reactions must take account of this environmental diversity. Ensemble-averaged variational transition state theory with multidimensional tunneling (EA-VTST/MT) was ...

Ab initio calculations of the potential energy surface for the C3(1Sigmag+)+C2H2(1Sigmag+) reaction have been performed at the RCCSD(T)/cc-pVQZ//B3LYP/6-311G(d,p) + ZPE[B3LYP/6-311G(d,p)] level with extrapolation to the complete basis set limit for key intermediates and products. These calculations have been followed by statistical calculations of reaction rate constants and product branching r...

Households First, I consider the individual consumption behaviour of households that operate in perfect financial markets and can borrow freely against the security of their future disposable labour income. In the body of the paper these are called permanent income consumers. Next aggregate consumption is derived on the assumption that all consumers are permanent income consumers. The final ste...