The ESCA molecule—Historical remarks and new results

Abstract

The C 1s photoelectron spectrum of ethyl trifluoroacetate (CF3COOCH2CH3), also known as the ‘ESCA molecule’, is the most illustrative showcase of chemical shifts in photoelectron spectroscopy. The binding energies of the four carbon atoms of this molecule spread over more than 8eV with energy separations ranging from 1.7 to 3.1eV owing to different chemical environments and hence different charge states of these atoms. The paper discusses history and importance of this spectrum in the field of photoelectron spectroscopy starting from the time of invention of the ESCA technique. The main focus of the paper is a ‘revisit’ of this spectrum using the most modern experimental and computational tools. Large geometrical changes, different for each ionization site, and the presence of two conformers of ethyl trifluoroacetate influence the spectral lineshapes of all four C 1s lines. These effects are carefully modeled by theory and investigated in the experimental spectrum.