Electronic structures and binding motifs of sodium polysulfide clusters NaS n - (n = 5-9): A joint negative ion photoelectron spectroscopy and computational investigation

We report a joint experimental and computational study on the electronic and geometric structures of a series of NaS_n^- (n = 5-9) clusters. Cryogenic, size-selective, negative ion photoelectron spectroscopy was employed to obtain their photoelectron spectra, in which distinctive spectral features with electron binding energy (EBE) up to 6.4 eV are unraveled. The EBE of the first peak in each spectrum for NaS_n^- (n = 5-9), assigned to the transition from the ground state of the anion to the ground state of each neutral radical, was observed to increase with cluster size. The vertical detachment energies (VDEs), measured from the first peak maximum, are 3.43 ± 0.02, 3.57 ± 0.02, 3.82 ± 0.03, 3.86 ± 0.02, and 4.00 ± 0.02 eV, and the adiabatic detachment energies (ADEs), determined from the onset of the first peak, are 3.27 ± 0.05, 3.44 ± 0.05, 3.65 ± 0.05, 3.75 ± 0.05, and 3.93 ± 0.05 eV, for n = 5-9, respectively. A number of low-lying isomers of the anions were screened and identified with density functional theory calculations, showing a structural preference of a chainlike polysulfide moiety electrostatically interacting with a sodium cation for all of the clusters. The CCSD(T)/aug-cc-pVTZ calculated VDEs and ADEs are in excellent agreement with the experimental results, confirming the identified isomers. Further analyses based on excited-state transitions, molecular orbitals, and natural population charges were performed, to assign and reveal the nature of all observed spectral bands. These computational results suggest that the electron detachment process and observed excitations are mainly derived from the polysulfide chain within each NaS_n^- cluster. This work provides a fundamental understanding of the intrinsic molecular properties of sodium polysulfide systems, which widely exist in life science and sodium-sulfur cells.