Slow photoelectron velocity-map imaging of cold and .

Abstract

High-resolution anion photoelectron spectra of cryogenically cooled C7 - and C9 - clusters obtained using slow photoelectron velocity-map imaging are presented, providing insight into the vibronic structure of neutral C7 and C9. These spectra yield accurate measurements of vibrational frequencies for the neutral clusters as well as electron affinities of 3.3517(4) and 3.6766(14) eV for C7 and C9, respectively. In the C7 - spectrum, transitions involving the previously unreported v 1 and v 2 symmetric stretching modes, as well as the v 9, v 10, and v 11 asymmetric bending modes, are assigned. Spin-orbit splitting is observed for several transitions in this spectrum, giving an energy difference of 28(6) cm-1 between the and spin-orbit levels of the C7 - anion. In the spectrum of C9 -, transitions involving the previously unreported symmetric stretch v 1 and the asymmetric bend v 11 are observed. In both spectra, several features are assigned to Franck-Condon forbidden transitions involving the doubly degenerate v 10 and v 11 modes of C7 and the v 13 and v 14 modes of C9. The appearance of these transitions is attributed to Herzberg-Teller coupling between the electronic states of the neutral clusters. Additional FC-forbidden transitions to states previously observed in gas-phase infrared experiments are observed and attributed to vibronic coupling between the electronic states of the anion, resulting in non-totally symmetric character in the anion's full vibrational ground state. Finally, consideration of the energy dependence of detachment cross sections and Dyson orbital analyses reveal that addition of more carbon atoms to the linear chain results in photodetachment from delocalized molecular orbitals with increasing nodal structure, leading to threshold photodetachment cross sections that differ considerably from simple symmetry considerations.