Simulation of Negative Ion Photoelectron Spectroscopy Using a Nuclear Ensemble Approach: Implications from a Nuclear...

The negative ion photoelectron spectroscopy (NIPES) has been proven to be a powerful technique to reveal the electronic structures and spectroscopic properties of various cluster anions/radicals with very high precision. However, direct comparisons of the theoretical NIPES with experimental measurements remain challenging. Particularly the nuclear vibration effect and the ionization probability are typically ignored in reproducing NIPES. In this work, the NIPES of three representative anions (NaS₅^-, P₂N₃^-, and HCPN₃^-) with significantly different spectral features were simulated by combining the nuclear ensemble approach (NEA) and Dyson orbitals (DOs). Overall, the simulated NIPES are in good agreement with the experimentally determined ones, confirming the robustness of such a strategy. The analysis of frontier molecular orbitals (MOs) and DOs further suggests the similar mixed characters for the first ionized doublet (D₀) and adjacent D₁ states of NaS₅^- with distributions on the side sulfur atoms. And the D₀ of P₂N₃* is confirmed as the lowest energy σ radical state; however, the D₀ of HCPN₃* should possess a mixture of π and σ electrons by taking into account the nuclear vibration effect. Next, the broader vibrational distribution and stronger main vibration modes of P₂N₃^- and HCPN₃^- explain why the nuclear vibration possesses a more pronounced influence in reproducing their NIPES while it has little effect on NaS₅^-. Last, the limitations based on the double-harmonic approximation model and density of state method were also discussed, highlighting that the ionization probability and orbital relaxation effect during the ionization process should be reasonably considered.