Abstract
It has been experimentally observed that water-ice-embedded polycyclic aromatic hydrocarbons (PAHs) form radical cations when exposed to vacuum UV irradiation, whereas ammonia-embedded PAHs lead to the formation of radical anions. In this study, we explain this phenomenon by investigating the fundamental electronic differences between water and ammonia, the implications of these differences on the PAH-water and PAH-ammonia interaction, and the possible ionization pathways in these complexes using density functional theory (DFT) computations. In the framework of the Kohn-Sham molecular orbital (MO) theory, we show that the ionic state of the PAH photoproducts results from the degree of occupied-occupied MO mixing between the PAHs and the matrix molecules. When interacting with the PAH, the lone pair-type highest occupied molecular orbital (HOMO) of water has poor orbital overlap and is too low in energy to mix with the filled π-orbitals of the PAH. As the lone-pair HOMO of ammonia is significantly higher in energy and has better overlap with filled π-orbitals of the PAH, the subsequent Pauli repulsion leads to mixed MOs with both PAH and ammonia character. By time-dependent DFT calculations, we demonstrate that the formation of mixed PAH-ammonia MOs opens alternative charge-transfer excitation pathways as now electronic density from ammonia can be transferred to unoccupied PAH levels, yielding anionic PAHs. As this pathway is much less available for water-embedded PAHs, charge transfer mainly occurs from localized PAH MOs to mixed PAH-water virtual levels, leading to cationic PAHs.