Structural Properties of Gas-Phase Solvated Electrons and Anions-Toward the Microscopic Understanding of Stabilization Mechanism-

The aim of the present research project was to attain a microscopic understanding of the stabilization mechanism at play in solvated electrons and anions through the systematic study about the electronic properties of gas-phase cluster anions in heterogeneous solvation environments.1。Reconstruction of the hydrogen-bonding network in(H_2O)_n^-：We demonstrated that the incorporation of a single D_2O or CH_3OH into(H_2O)_&lt；6，7&gt；^-proceeded efficiently without losing any H_2O constituent，by exploiting the“Ar-mediated”process such as(H_2O)_n^-Ar_m+M→[M·(H_2O)_n^^→[(H_2O)_nM]-+mAr.The photoelectron spectroscopic measurements revealed that isomeric interconversion occurred in[(H_2O)_nM]^-through an extensive reconstruction of the hydrogen-bonding network during the incorporation processes.2.Formation and photodestruction of dual dipole-bound anion：A new type of dipole-bound anion composed of water and a polar molecule withµ&gt；2.8D was generated by the incorporation reaction…More of argon-solvated water hexamer anions，(H_2O)_6^-Ar_m.The newly-found anion can be regarded as a dual dipole-bound species described as(H_2O)_6{e^-}M，where the diffuse excess electron interacts with both(H_2O)_6 and M via the individual electron-dipole interaction.The dual dipole-bound anion also serves as a precursor to the hydrated valence anion of M.3。Structures of[(CO_2)_n(ROH)_m]^-(R=H，CH_3)cluster anions：The solvation structures of[(CO_2)_n(ROH)_m]^-were investigated by infrared photodissociation spectroscopy combined with ab initio calculations.A significant entrainer effect was observed such that the incorporated protic molecule stabilizes CO_2effectively through the single ionic hydrogen-bonding interaction.4。Valence anions stabilized by surrounding multi-dipoles：The electronic properties of the negatively-charged clusters of acetone and water molecules，[(Me_2CO)_n(H_2O)_m]^-，were studied by photoelectron imaging spectroscopy.The measurement indicates possibility that a new type of stabilization mechanism is operative in[(Me_2CO)_n(H_2O)_m]^-：i.e.，the valence anion of Me_2CO is stabilized by an electrostatic field generated by the surrounding multi-dipoles。Less：Less

The aim of the present research project was to attain a microscopic understanding of the stabilization mechanism at play in solvated electrons and anions through the systematic study about the electronic properties of gas-phase cluster anions in heterogeneous solvation environments.1. Reconstruction of the hydrogen-bonding network in (H_2O)_n^-: We demonstrated that the incorporation of a single D_2O or CH_3OH into (H_2O)_<6,7>^-proceeded efficiently without losing any H_2O constituent, by exploiting the "Ar-mediated" process such as (H_2O)_n^-Ar_m+M→[M・(H_2O)_n^-Ar_m]^†→[(H_2O)_nM]^-+mAr. The photoelectron spectroscopic measurements revealed that isomeric interconversion occurred in [(H_2O)_nM]^-through an extensive reconstruction of the hydrogen-bonding network during the incorporation processes.2. Formation and photodestruction of dual dipole-bound anion: A new type of dipole-bound anion composed of water and a polar molecule with μ>2.8 D was generated by the incorporation reaction … More of argon-solvated water hexamer anions, (H_2O)_6^-Ar_m. The newly-found anion can be regarded as a dual dipole-bound species described as (H_2O)_6{e^-} M, where the diffuse excess electron interacts with both (H_2O)_6 and M via the individual electron-dipole interaction. The dual dipole-bound anion also serves as a precursor to the hydrated valence anion of M.3. Structures of [(CO_2)_n(ROH)_m]^-(R=H, CH_3) cluster anions: The solvation structures of [(CO_2)_n(ROH)_m]^-were investigated by infrared photodissociation spectroscopy combined with ab initio calculations. A significant entrainer effect was observed such that the incorporated protic molecule stabilizes CO_2 effectively through the single ionic hydrogen-bonding interaction.4. Valence anions stabilized by surrounding multi-dipoles: The electronic properties of the negatively-charged clusters of acetone and water molecules, [(Me_2CO)_n(H_2O)_m]^-, were studied by photoelectron imaging spectroscopy. The measurement indicates possibility that a new type of stabilization mechanism is operative in [(Me_2CO)_n(H_2O)_m]^-: i. e., the valence anion of Me_2CO is stabilized by an electrostatic field generated by the surrounding multi-dipoles. Less