Site-Selective Dissociation Processes of Cationic Ethanol Conformers: The Role of Hyperconjugation.

The journal of physical chemistry. A

PubMedID: 25080068

Li W, Hu Y, Liu F, Shan X, Sheng L. Site-Selective Dissociation Processes of Cationic Ethanol Conformers: The Role of Hyperconjugation. J Phys Chem A. 2014;.
In present report, we explored hyperconjugation effects on the site- and bond-selective dissociation processes of cationic ethanol conformers by the use of theoretical methods (including configuration optimizations, natural bond orbital (NBO) analysis and Density of States (DOS) calculations et al.) and the tunable synchrotron vacuum ultraviolet (SVUV) photoionization mass spectrometry. The dissociative mechanism of ethanol cations, in which hyperconjugative interactions and charge-transfer processes were involved, was proposed. The results reveal Ca-H and C-C bonds are selectively weakened, which arise as a result of the hyperconjugative interactions sCa-H ? p in trans-conformer and sC-C ? p in gauche-conformer after being ionized. As a result, the selective bond cleavages would occur and different fragments were observed.