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A Simple ab Initio Model for the Hydrated Electron That Matches Experiment
- Source :
- The Journal of Physical Chemistry A. 119:9148-9159
- Publication Year :
- 2015
- Publisher :
- American Chemical Society (ACS), 2015.
-
Abstract
- Since its discovery over 50 years ago, the “structure” and properties of the hydrated electron has been a subject for wonderment and also fierce debate. In the present work we seriously explore a minimal model for the aqueous electron, consisting of a small water anion cluster embedded in a polarized continuum, using several levels of ab initio calculation and basis set. The minimum energy zero “Kelvin” structure found for any 4-water (or larger) anion cluster, at any post-Hartree-Fock theory level, is very similar to a recently reported embedded-DFT-in-classical-water-MD simulation (UMJ: Uhlig, Marsalek, and Jungwirth, Journal of Physical Chemistry Letters 2012, 3, 3071-5), with four OH bonds oriented toward the maximum charge density in a small central “void”. The minimum calculation with just four water molecules does a remarkably good job of reproducing the resonance Raman properties, the radius of gyration derived from the optical spectrum, the vertical detachment energy, and the hydration free energy. For the first time we also successfully calculate the EPR g-factor and (low temperature ice) hyperfine couplings. The simple tetrahedral anion cluster model conforms very well to experiment, suggesting it does in fact represent the dominant structural motif of the hydrated electron.
- Subjects :
- Rotation
Chemistry
Molecular Conformation
Ab initio
Water
Charge density
Electrons
Hydrogen Bonding
Electron
Molecular Dynamics Simulation
Solvated electron
Article
Ion
Molecular dynamics
Radius of gyration
Quantum Theory
Thermodynamics
Physics::Chemical Physics
Physical and Theoretical Chemistry
Atomic physics
Basis set
Subjects
Details
- ISSN :
- 15205215 and 10895639
- Volume :
- 119
- Database :
- OpenAIRE
- Journal :
- The Journal of Physical Chemistry A
- Accession number :
- edsair.doi.dedup.....2f104386c02f0dbc2bfb07615179da9e