Reassignment of the Photoelectron Spectrum of Methylketene Using a Hybrid Model of Harmonic and Anharmonic Oscillators to Compute Franck–Condon Factors

Abstract

We constructed a hybrid model of harmonic and anharmonic oscillators to compute Franck–Condon factors and interpret the photoelectron spectrum of methylketene. The equilibrium structures of methylketene and its cation were optimized, and then, the harmonic and anharmonic vibrational frequencies were computed using the B3LYP, PBE0, APFD, and ωB97XD approaches of the density functional theory. The photoelectron spectrum of methylketene was simulated by computing the Franck–Condon factors with both the harmonic and hybrid models. The adiabatic ionization energy of methylketene was computed by using the CCSD­(T) approach extrapolating to the complete basis set limit. The simulated photoelectron spectra are consistent with those from the experiment for both the harmonic and hybrid models. However, the error in band positions is reduced by using the hybrid model. The computed adiabatic ionization energies of methylketene are in agreement with the experiment, with the smallest error being 0.017 eV. Our interpretation based on the theoretical spectrum led to the reassignment of the experimental photoelectron spectrum of methylketene.