The dissociation rate constants for hydrogen fluoride dimers are calculated using the YL method, proposed by Yao and Lin (Yao, L.; Mebel, A. M.; Lu, H. F.; Neusser, H. J.; Lin, S. H. J. Phys. Chem. A 2007, 111, 6722). The dividing surface method and RRKM theory are also used to obtain pseudo-transition states and rate constants, respectively. For the dissociation of HF dimers, the anharmonic ra...

Abstract A single-pulse shock tube study of the four pentene isomers is carried out at 2?±?0.16?bar and 900–1600?K. C1 to C6 species profiles were recorded using gas chromatography mass spectrometry analyses. The are identified quantified by flame ionization detection. High-pressure limiting pressure-dependent rate constants for 2M1B, 2M2B 3M1B?+?? calculated RRKM theory with a Master Equation ...

Unimolecular rate theory for various types of reactions is implemented for any looseness of transition state. Quantum states are counted for all but the ‘‘transitional’’ modes, their phase space being counted via Monte Carlo sampling. The rate constant kEJ is then weighted with the initial E and J distributions. 2013 Elsevier B.V. All rights reserved.

The major tropospheric removal process for hexafluorobenzene is its oxidation by hydroxyl (OH) radicals. However, there is no information on the reaction mechanism of this important process. All geometries and energies significant for the tropospheric degradation of hexafluorobenzene were characterized using the MP2/6-311+G(d,p) and/or G3 methods. It was found out that the addition of OH radica...

A theory is described for the variation in the rate constants for formation of different ozone isotopomers from oxygen atoms and molecules at low pressures. The theory is implemented using a simplified description which treats the transition state as loose. The two principal features of the theory are a phase space partitioning of the transition states of the two exit channels after formation o...

The large kinetic discrepancy between computational and experimental studies is resolved using the rigorous stochastic RRKM-based master-equation rate model. Detailed mechanistic insights are also revealed to advance its related applications.

To provide an objective measure of the correlation between the internal energy content of ions generated by matrix-assisted laser desorption/ionization (MALDI) and the matrix properties, a series of well-characterized benzyl-substituted benzylpyridinium salts were used as thermometer molecules (TMs). To determine the internal energy variations of analyte ions, the survival yields of TM molecula...

Abstract Rate coefficients for elementary reactions connected to the potential energy wells of SiHCl 3 , SiH 2 Cl and Cl, which are important Si 1 species in chemical vapor deposition (CVD) processes that use chlorosilanes as silicon source gases, were determined through Rice–Ramsperger–Kassel–Marcus (RRKM) theory various conditions temperature pressure. Many unimolecular decomposition channels...