The chemical reaction dynamics to form cyanoacetylene, HCCCN (X S), via the radical–neutral reaction of cyano radicals, CN(X S;n50), with acetylene, C2H2(X Sg ), are unraveled in crossed molecular beam experiments at two collision energies of 21.1 and 27.0 kJ mol. Laboratory angular distributions and time-of-flight spectra of the HCCCN product are recorded at m/e551 and 50. Experiments were sup...

Cyclic ethers (CEs) can be promising future biofuel candidates. Most CEs possess physico-chemical and combustion indicators comparable to conventional fuels, making them suitable for internal engines. This work computationally investigates the kinetic behaviors of hydrogen abstraction from 2-methyl tetrahydrofuran (2MTHF), one CEs, by hydroxyl radicals under atmospheric relevant conditions. The...

The computation, starting from basic principles, of chemical reaction rates in realistic systems (with three or more degrees of freedom) has been a longstanding goal of the chemistry community. Our current work, which merges tube dynamics with Monte Carlo methods provides some key theoretical and computational tools for achieving this goal. We use basic tools of dynamical systems theory, mergin...

The unimolecular decomposition of CH3CH2OH has been investigated at the G2M (RCC2) level of theory. The decomposition reaction was found to be dependent strongly on pressure and temperature. Among the 8 product channels identified, the H2O-elimination process (1) via a four-member-ring transition state is dominant below 10 atm in the temperature range of 700 – 2500 K. At the high – pressure lim...

Energy selected mono-, di- and trimethylamine ions were prepared by threshold photoelectron photoion coincidence spectroscopy (TPEPICO). Below 13 eV, the main dissociative photoionization path of these molecules is hydrogen atom loss. The ion time-of-flight (TOF) distributions and breakdown diagrams for H loss are analyzed in terms of the statistical RRKM theory, which includes tunneling. Exper...

The kinetics and mechanisms for the unimolecular decomposition reactions of formic acid and oxalic acid have been studied computationally by the high-level G2M(CC1) method and microcanonical RRKM theory. There are two reaction pathways in the decomposition of formic acid: The dehydration process starting from the Z conformer is found to be the dominant, whereas the decarboxylation reaction star...

The pyrolysis of ethylene glycol vinyl ether (EGVE), an initial product of 1,4-dioxane dissociation, was examined in a diaphragmless shock tube (DFST) using laser schlieren densitometry (LS) at 57 ± 2 and 122 ± 3 Torr over 1200-1800 K. DFST/time-of-flight mass spectrometry experiments were also performed to identify reaction products. EGVE was found to dissociate via two channels: (1) a molecul...

Unimolecular dissociation of 1,3,5-trioxane was investigated experimentally and theoretically over a wide range of conditions. Experiments were performed behind reflected shock waves over the temperature range of 775-1082 K and pressures near 900 Torr using a high-repetition rate time of flight mass spectrometer (TOF-MS) coupled to a shock tube (ST). Reaction products were identified directly, ...

The reaction of 2,5-dimethylfuran (DMF) with H-atoms was studied using a potential energy surface calculated at the CBS-QB3 level of theory and master equation/RRKM modeling. Hydrogen abstraction by H-atom and hydrogen additions on DMF were considered. As the decomposition pathways of the initial adducts were unknown, a large number of decomposition routes was explored for these adducts. An imp...

The mechanisms and kinetics of unimolecular decomposition of succinic acid and its anhydride have been studied at the G2M(CC2) and microcanonical RRKM levels of theory. It was shown that the ZsgsZ conformer of succinic acid, with the Z-acid form and the gauche conformation around the central C-C bond, is its most stable conformer, whereas the lowest energy conformer with the E-acid form, ECGsZ,...