ACTIVATION OF SINGLE-BUBBLE SONOLUMINESCENCE AND RADIOLUMINESCENCE OF GD3+ AND DY3+ IONS BY ELECTRON ACCEPTORS IN AQUEOUS SOLUTIONS AS CONSEQUENCE OF THE HYDRATED ELECTRON GENERATION DURING WATER SONOLYSIS AND RADIOLYSIS

Discovered the activation of moving single-bubble sonoluminescence and radioluminescence for Gd3+ and Dy3+ ions in aqueous solutions of GdCl3 and DyCl3 by the acceptor of a hydrated electron (eaq-): H+, Cd2+, etc. This activation is similar to the previously found activation by acceptors of eaq- radioluminescence and single-bubble sonoluminescence for the Tb3+ ion. Electron acceptors do not affect the quantum yield of the said lantha-nide ions photoluminescence. They also do not affect the yield of their multibubble sonoluminescence in aqueous solutions, since eaqdoes not appear in significant amounts during multibubble sonolysis. The found luminescence activation effects of lanthanide ions are interpreted as a consequence of the suppression of the quenching (reduction) reactions of these electronically excited ions eaq: *Ln3+ + eaq- → Ln2+ by acceptors. The feasibility of these reactions was predicted for all Ln3+ ions based on a theoretical estimate of their free energy. The discovery of the described effects of activation of the luminescence of Ln3+ ions is a consequence and serves as confirmation of not only the known generation of eaq- during radiolysis, but also its previously unknown generation during moving single-bubble sonolysis of water.

Flexible boundary layer using exchange for embedding theories. II. QM/MM dynamics of the hydrated electron

The FlexiBLE embedding method introduced in the preceding companion paper [Z. Shen and W. J. Glover, J. Chem. Phys. X, X (2021)] is applied to explore the structure and dynamics of the aqueous solvated electron at an all-electron density functional theory QM/MM level. Compared to a one-electron mixed quantum/classical description, we find the dynamics of the many-electron model of the hydrated electron exhibits enhanced coupling to water OH stretch modes. Natural Bond Orbital analysis reveals this coupling is due to significant population of water OH σ* orbitals, reaching 20%. Based on this, we develop a minimal frontier orbital picture of the hydrated electron involving a cavity orbital and important coupling to 4-5 coordinating OH σ* orbitals. Implications for the interpretation of the spectroscopy of this interesting species are discussed.

Flexible boundary layer using exchange for embedding theories. II. QM/MM dynamics of the hydrated electron

The FlexiBLE embedding method introduced in the preceding companion paper [Z. Shen and W. J. Glover, J. Chem. Phys. X, X (2021)] is applied to explore the structure and dynamics of the aqueous solvated electron at an all-electron density functional theory QM/MM level. Compared to a one-electron mixed quantum/classical description, we find the dynamics of the many-electron model of the hydrated electron exhibits enhanced coupling to water OH stretch modes. Natural Bond Orbital analysis reveals this coupling is due to significant population of water OH σ* orbitals, reaching 20%. Based on this, we develop a minimal frontier orbital picture of the hydrated electron involving a cavity orbital and important coupling to 4-5 coordinating OH σ* orbitals. Implications for the interpretation of the spectroscopy of this interesting species are discussed.

Flexible boundary layer using exchange for embedding theories. II. QM/MM dynamics of the hydrated electron

The FlexiBLE embedding method introduced in the preceding companion paper [Z. Shen and W. J. Glover, J. Chem. Phys. X, X (2021)] is applied to explore the structure and dynamics of the aqueous solvated electron at an all-electron density functional theory QM/MM level. Compared to a one-electron mixed quantum/classical description, we find the dynamics of the many-electron model of the hydrated electron exhibits enhanced coupling to water OH stretch modes. Natural Bond Orbital analysis reveals this coupling is due to significant population of water OH σ* orbitals, reaching 20%. Based on this, we develop a minimal frontier orbital picture of the hydrated electron involving a cavity orbital and important coupling to 4-5 coordinating OH σ* orbitals. Implications for the interpretation of the spectroscopy of this interesting species are discussed.