Abstract
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.
Supplementary materials
Title
Supplementary Material
Description
Explanation of DFT grid errors when using floating Gaussian basis functions, and further details on our NBO analysis and model Hamiltonian.
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