AB INITIO/RRKM APPROACH TOWARD THE UNDERSTANDING OF ETHYLENE PHOTODISSOCIATION
Loading...
Date
1998
Journal Title
Journal ISSN
Volume Title
Publisher
Ohio State University
Abstract
The optimized structures and harmonic frequencies for the transition states and intermediates on the ground state potential energy surfaces of ethylenes, including $C_{2}H_{4}, C_{2}D_{4}, D_{2}CCH_{2}$. cis- and trans-HDCCDH, related to the molecular and atomic hydrogen elimination channels of photodissociation in VUV were characterized at the B3L YP/6-311G(d.p) level. The coupled cluster method, CCSD(T)/6-311+G(3df,2p), was employed to calculate the corresponding energies with the zero-point energy corrections by the B3LYP/6-311G(d,p) approach. Ethylidene was found to be an intermediate in the $1,2 - H_{2}$ elimination channel. The barrier for the $1,1 - H_{2}$ elimination was computed to be the lowest (4.10-4.16 eV), while the $1,2 - H_{2}$ elimination and H loss channels have barriers of a similar height (4.70-4.80 eV). The rate constant for each elementary step of ethylene photodissociation at 193 and 157 nm was calculated according to the RRKM theory based on the ab initio surfaces. The rate equations were subsequently solved, and thus the concentration of each species was obtained as a function of time. The concentrations $t \to \infty$ were taken for calculating branching ratios or yields. In accord with previous experimental findings, the calculated branching ratio for the $1,1 - H_{2}$ elimination process is higher than that for the $1,2 - H_{2}$ elimination, and the atomic elimination channel is predicted to be favored at increasing excitation energy when competing with the molecular elimination. The significant discrepancies between theoretical and experimental results in the magnitude of the yields and their dependence on the wavelength for the molecular elimination channels suggest the dynamics of either $1,2 - H_{2}$, or $1,1 - H_{2}$ elimination, or both channels may be non-statistical in nature.
Description
Author Institution: Institute of Atomic And Molecular Sciences, Academia Sinica