Conformational effects in inner-shell photoelectron spectroscopy of ethanol -: art. no. 103002

The carbon 1s photoelectron spectrum of ethanol shows two peaks, one for the methyl carbon and one for the functionalized carbon. While the peak shape for the functionalized carbon is readily understood, the shape for the methyl carbon requires that there be comparable contributions from both the anti and gauche conformers of ethanol and that the torsional motion in the HOCC dihedral angle be strongly excited upon core ionization. An accurate description of the peak shape requires a high level of electronic-structure theory together with consideration of anharmonicity and coupling of the torsional motion with other vibrational modes.