Ab initio Study of Alkyl-oxonium Cations CnH2n+1OH2+, n=1,2,3,4

[摘要] Within the framework of the itinerant radical model, the solvated electron in liquid alcohols is understood as an itinerant alkyl-oxonium ROH₂. radical. As a first step in the investigation of those radicals, this study deals with the optimization of related ROH₂⁺ alky-oxonium cations: C_nH_2n+1OH₂⁺,n=1,2,3,4. The structures were optimized at the MP2/6-31G**++ level with the help of the GAMESS ab initio package. Optimized structures are reported for the following cations: MethylOxonium; EthylOxonium; 1-PropylOxonium, 2-PropylOxonium and 1-ButylOxonium, 2-ButylOxonium, IsoButylOxonium, TertButylOxonium. Optimized geometries are displayed with the help of the ChemApp Java applet. Vibrational frequencies and ZPEs have been computed, and visual depictions of expected experimental IR spectra have been simulated with the help of Lorentzian functions.

[关键词] Alcohols;Oxonium cations;AlkylOxonium;MethylOxonium;EthylOxonium;PropylOxonium;PropylOxonium;ButylOxonium;Ab initio;GAMESS;CaChe;SMILES;CORINA;Itinerant Radical model;Solvated Electron;Radiation Chemistry;ChemApp;Java Applet