Probing the electronic structure and ground state symmetry of gas phase C60+ via VUV photoionization and comparison with theory.

ABSTRACT

Recently, some of us reviewed and studied the photoionization dynamics of C60 that are of great interest to the astrochemical community as four of the diffuse interstellar bands (DIBs) have been assigned to electronic transitions in the C60+ cation. Our previous analysis of the threshold photoelectron spectrum (TPES) of C60 [Hrodmarsson et al., Phys. Chem. Chem. Phys. 22, 13880-13892 (2020)] appeared to give indication of D3d ground state symmetry, in contrast to theoretical predictions of D5d symmetry. Here, we revisit our original measurements taking account of a previous theoretical spectrum presented in the work of Manini et al., Phys. Rev. Lett. 91(19), 196402 (2003), obtained within a vibronic model parametrized on density functional theory/local-density approximation electronic structure involving all hg Jahn-Teller active modes, which couple to the 2Hu components of the ground state of the C60+ cation. By reanalyzing our measured TPES of the ground state of the C60 Buckminsterfullerene, we find a striking resemblance to the theoretical spectrum calculated in the work of Manini et al., Phys. Rev. Lett. 91(19), 196402 (2003), and we provide assignments for many of the hg modes. In order to obtain deeper insights into the temperature effects and possible anharmonicity effects, we provide complementary modeling of the photoelectron spectrum via classical molecular dynamics (MD) involving density functional based tight binding (DFTB) computations of the electronic structure for both C60 and C60+. The validity of the DFTB modeling is first checked vs the IR spectra of both species which are well established from IR spectroscopic studies. To aid the interpretation of our measured TPES and the comparisons to the ab initio spectrum we showcase the complementarity of utilizing MD calculations to predict the PES evolution at high temperatures expected in our experiment. The comparison with the theoretical spectrum presented in the work of Manini et al., Phys. Rev. Lett. 91(19), 196402 (2003), furthermore, provides further evidence for a D5d symmetric ground state of the C60+ cation in the gas phase, in complement to IR spectroscopy in frozen noble gas matrices. This not only allows us to assign the first adiabatic ionization transition and thus determine the ionization energy of C60 with greater accuracy than has been achieved at 7.598 ± 0.005 eV, but we also assign the two lowest excited states (2E1u and 2E2u) which are visible in our TPES. Finally, we discuss the energetics of additional DIBs that could be assigned to C60+ in the future.