Photoionization of atom-fullerene hybrid levels in F@C$_{\mathrm{60}}$ versus F$^{\mathrm{-}}$@C$_{\mathrm{60}}^{\mathrm{+}}$.

A density functional study to model the ground state structure and to calculate the photoionization properties of the F@C$_{\mathrm{60}}$ endohedral molecule is performed. The method goes beyond the local density approximation by employing the Leeuwen-Baerends (LB) exchange-correlation functional [1] and the interaction of the molecule with the radiation field is described in a linear response framework [2]. The study primarily focusses on the photodynamics of atom-fullerene hybrid levels of $p $angular momentum character. It is found that this hybridization is weak for F@C$_{\mathrm{60}}$ as well as for F$^{\mathrm{-}}$@C$_{\mathrm{60}}^{\mathrm{+}}$ formed after an electron transfers to F from most any of the C$_{\mathrm{60}}$ levels. However, when this electron originates from the C$_{\mathrm{60}}$ hybridizing level itself, the hybridization is strengthened dramatically. This contradicted the hole-level universality found for Cl$^{\mathrm{-}}$@C$_{\mathrm{60}}^{\mathrm{+}}$ earlier [3]. Consequently, significant variations in photoionization cross sections at the plasmonic energies of the spectrum and beyond emerge. Detailed results will be presented in the conference. [1] R. Van Leeuwen and E. J. Baerends, \textit{Phys. Rev. A} \textbf{49}, 2421 (1994); [2] M. E. Madjet \textit{et al}., \textit{J. Phys. B} \textbf{41}, 105101 (2008); [3] D. Shields, R. De, M. E. Madjet, S. T. Manson, and H. S. Chakraborty (submitted) \underline {arXiv:1907.04881}~ [physics.atm-clus].