Vibrationally-Resolved X-ray Photoelectron Spectra of Six Polycyclic Aromatic Hydrocarbons from First-Principles Simulations

Abstract

Vibrationally resolved C 1s X-ray photoelectron spectra (XPS) of a series of six polycyclic aromatic hydrocarbons (PAHs; phenanthrene, coronene, naphthalene, anthracene, tetracene, and pentacene) were computed by combining the full core hole density functional theory and the Franck−Condon simulations with the inclusion of the Duschinsky rotation effect. Simulated spectra of phenanthrene, coronene, and naphthalene agree well with experiments both in core binding energies (BEs) and profiles, which validate the accuracy of our predictions for the rest molecules with no high-resolution experiments. We found that three types of carbons i (inner C), p (peripheral C bonded to three C atoms), and h (peripheral C bonded to an H atom) show decreasing BEs. In linear PAHs (the latter four), h-type carbons further split into h1 or h2 (on inner or edge benzene ring) subtypes with chemical shifts of ca. 0.2−0.4 eV. All major Franck− Condon-active modes are characterized to be in-plane vibrations: low-frequency (<800 cm −1 ) C−C ring deformation modes play an essential role in determining the peak asymmetries; and for each h-type carbon a high-frequency (ca. 3600 cm −1 ) C*−H stretching mode is responsible for the high-energy tail. We found that core ionization leads to reduction of all C*−C and C*−H bond lengths and ring deformation with a definite direction. Based on theoretical spectra of four linear PAHs, we found asymptotic relations and anticipated possible spectral features for even larger linear PAHs. Our calculations provide accurate reference spectra for XPS characterizations of PAHs, which are useful in understanding the vibronic coupling effects in this family.

Chemical Doping by Fluorination and Its Impact on All Energy Levels of π-Conjugated Systems

“…The calculated fine structure components of the C1s ionization energies of PEN molecules are in excellent agreement with previous theoretical works. 54,55 Similarly, also the C−F-related C1s core levels reveal a fine structure for the various carbon atoms near the fluorination position, which is sometimes referred to as a second-order chemical shift. While the current experimental energy resolution does not allow us to resolve such fine structures of the C−C/C-H and C−F sublevels, as was possible in previous high-resolution XPS measurements for PEN, 54 all calculated ionization energies (see SI, Tables S2−S14) have been broadened by Gaussians (σ = 0.35 eV) to allow comparison with the measured XPS signatures.…”