Molecular and cluster anions have been investigated using a newly built tandem time-of-flight mass spectrometer combined with photoelectron imaging system. Solvation particularly hydration is shown not only to stabilize metastable anions such as CO₂⁻ in their ground state and impede autodetachment but also to alter the dynamics in the excited states. For instance, the 355 nm photoelectron image of mass-selected CO₂⁻(H₂O)(m) evolves from anisotropic to isotropic as m increases indicating excited state decay via electron autodetachment. Dissociation channels open at m=2 at 266 nm, resulting in O−(H₂O)m-k and CO₂⁻(H₂O)(m-k) products, the later becoming dominant as m increases. The photoelectron imaging of (CS₂)₂⁻ has revealed the coexistence of four electronic isomers: CS₂⁻•CS₂ [C(s)(₂A′)] and three covalent C₂S₄⁻ [C₂ᵥ(²B₁), D(2h)(²B(3g)), and D(2d)( ²A₁)] structures. Water-mediated intermolecular interactions have been shown to facilitate the formation of the global minimum C₂ᵥ(²B₁) structure rather than the less stable local minima C(s)(₂A′) and D(2d)(²A₁) structures that are favored in the dry source condition. In the (CS2)(n)⁻, n ≥ 3 and (CS₂)₂⁻ (H₂O)(m), m > 0 clusters, the population of the C₂ᵥ(²B₁) structure diminishes drastically due to more favorable solvent interactions with the CS2 − monomercore. Photoexcitation of the (CS₂)₂⁻ also results in the formation of CS₂⁻ and C₂S₂⁻ at 532 nm, and C₂S₂⁻, CS₂⁻, CS₃⁻, S₂⁻, and S⁻ at 355 and 266 nm. The relative yields of C₂S₂⁻ is significantly higher when (CS₂)₂⁻ is formed under wet source condition suggesting C₂ᵥ(²B₁) structure as the origin of C₂S₂⁻. An abrupt decrease in the relative yield of C₂S₂⁻ is observed upon adding CS₂ or H₂O to (CS₂)₂⁻. The CS₂⁻ based clusters are the likely origin of the S− photoproduct, while CS₃⁻ is formed through the secondary S⁻+CS₂ reaction. Novel anions (CS₂O₂⁻ and CS₃O⁻) are observed in the CS₂+O₂+e⁻ reaction. The photoelectron imaging and photodissociation results of these and other anionic products are presented. In addition, CS₂⁻•O₂ ion-neutral complex is formed depending on the conditions in the ion source. Despite the positive electron affinity of O₂, no clear signature of O₂⁻•CS₂ ion-neutral complex is seen in the photoelectron image. CO₃⁻ ion is also formed abundantly as a result of CS₂+CO₂+O₂+e⁻ reaction
