Time-Dependent Density Functional Theory Study of the X-ray Absorption Spectroscopy of Acetylene, Ethylene, and Benzene on Si(100)

The carbon 1s X-ray absorption spectroscopy (XAS) of acetylene, ethylene, and benzene in gas phase and adsorbed on the Si(100) surface is studied using time-dependent density functional theory (TDDFT) with hybrid exchange correlation functionals. The computed spectra are sensitive to the proportion of Hartree−Fock exchange in the exchange-correlation functional. The fraction of Hartree−Fock exchange is optimized to provide accurate predictions of the 1s → π* excitation energies. In gas phase, the spectra of acetylene, ethylene and benzene are dominated by 1s → π* excitations with further weaker bands at higher energies below the ionization threshold arising predominantly from Rydberg excitations. In the spectrum for ethane, bands arising from excitation to Rydberg and excitations are observed. For the molecules adsorbed on Si(100), excitations to Rydberg states are less evident. The calculations indicate that acetylene adsorbed on the Si(100) surface has an intense π* band, which lies 1.5 eV lower than in...

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