Computational Study of Mechanism Thermal Decomposition of unimolecular reactions of Vinyl Ethers Based on Computer modeling

: In this study, a detailed theoretical study was conducted based on the mechanism of thermal unimolecular decay of vinyl propyl ether(VPE) , vinyl isopropyl ether(VIPE) and vinyl butyl ether(VBE) and a practical approach is offered, based on the application of molecular mechanics and Gaussian programs developed for the calculation of structure and properties of molecular system. Moreover, the application of VPE, VIPE and VBE have shown that only one type of several possible alternatives of the intermolecular proton transferring (IPT) between α- hydrogen atoms for VPE , Bean for VIPE between β -hydrogen atom of alkyl groups exists with the extreme carbon atom of the vinyl group leading to the thermal decay of ethers under study. The satisfactory agreement between the activation energies calculated for the decomposition of vinyl ethers and the experimental data also shows that the component resulting from the formation of anti bonding orbitals makes the main contribution to the energy of deformation upon the formation of the cyclic structure via hydrogen bridges, and other possible types of molecular interactions do not contribute appreciably. The developed approach enables the computing of frequency values, leading to the decay of the vinyl ether molecule, thus providing the basis for the calculation of the rate constant value and the determination of its pressure dependency. The new results obtained through computational methods, as well as their satisfactory juxtaposition with the experimental results are indicative of the correctness of the offered approach and its application in complex systems that are demanding in terms of precise calculation.