Structural and electronic properties of HCnS− (n = 4–11): anion photoelectron spectroscopy and density functional calculations

Abstract

We investigated the HC_nS⁻ (n = 4–11) clusters using anion photoelectron spectroscopy and density functional theory calculations. The partially resolved vibrational spectra of the HC_nS⁻ (n = 4–11) clusters are obtained. We found that the vertical detachment energies of the HC_nS⁻ (n = 4–11) clusters display an obvious parity effect with increasing number of carbon atoms: the vertical detachment energies of the even-numbered HC_nS⁻ are higher than their neighboring odd-numbered counterparts; the spectral features of the even-numbered HC_nS⁻ are much sharper than those of their odd-numbered counterparts. The ground-state structures of the anionic and neutral HC_nS (n = 4–11) clusters are linear with the H and S atoms locating at two ends of the carbon chain. The electron affinities of the neutral HC_nS (n = 4–11) clusters are determined based on the transitions from the ground states of HC_nS⁻ anions to the electronic ground states of HC_nS neutral species.