Comparison of Photoelectron-Spectroscopy Results to Ab-Initio and Density Functional Calculations: The Ethylbenzene Cation

Abstract

In this work resonant S 0–S 1 two-photon ionization (R2PI) and high-resolution R(1+1’)PI photoelectron spectroscopy (PES) as well as ab initio and density functional (DFT) calculations of ethylbenzene (EB) are combined. Conformer energies and equilibrium geometries have been calculated for neutral and cationic EB with the HF, UHF, B3LYP and the MP2 methods and different basis sets. In agreement with previous results the tail-to-chromophore orientation of neutral EB is orthogonal. This conformer is also the most stable structure in the cation, but a second local minimum in which all carbons lie in a plane (termed “planar” conformer) lays 325cm-1 higher in energy. R(1+1’)PI PE spectra were recorded by time-of-flight spectrometer with an energy resolution (Δ E) below 8 cm-1 and an absolute accuracy of ± 10 cm-1 for electron energies below 200 meV. Because the experiment starts in the orthogonal conformer and ionization is vertical, the recorded PE spectra show the cation ground state vibrations of this conformer. Beside benzene modes also low-energetic tail-to-chromophore modes are observed and assigned by DFT vibrational mode analysis. The differences of the calculated vibrational frequencies between the two conformers are comparable to the deviation between experiment and theory and a conformer assignment by comparison of theory and experiment would be difficult. R(1+1’)PI PE spectra recorded via selected S 1 vibrations provide vibrational assignments for S 1, qualitative S 1–D 0 geometry changes, vibrational symmetries as well as internal vibrational redistribution dynamics in S 1. Charge and spin densities of the neutral and cation were calculated to elucidate the problem of charge delocalization and electronic tail-to-chromophore coupling.