Abstract
The adiabatic bound state of an excess electron is calculated for a water cluster (H2O) −8 in the gas phase using the DFT-B3LYP method with the extended 6-311++G(3df,3pd) basis set. For the liquid phase the calculation is performed in the polarizable continuum model (PCM) with regard to the solvent effect (water, ɛ = 78.38) in the supermolecule-continuum approximation. The value calculated by DFT-B3LYP for the vertical binding energy (VBE) of an excess electron in the anionic cluster (VBE(H2O) −8 = 0.59 eV) agrees well with the experimental value of 0.44 eV obtained from photoelectron spectra in the gas phase. The VBE value of the excess electron calculated by PCM-B3LYP for the (H2O) −8 cluster in the liquid phase (VBE = 1.70 eV) corresponds well to the absorption band maximum λmax = 715 nm (VBE = 1.73 eV) in the optical spectrum of the hydrated electron hydr e −hydr . Estimating the adiabatic binding energy (ABE)e t-hydr in the (H2O) −8 cluster (ABE = 1.63 eV), we obtain good agreement with the experimental free energy of electron hydration ΔG 0298 (e −hydr ) = 1.61 eV. The local model (H2O) 2−8 of the hydrated dielectron is considered in the supermolecule-continuum approximation. It is shown that the hydrated electron and dielectron have the same characteristic local structure: -O-H{↑}H-O- and -O-H{↑↓}H-O-respectively.
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Original Russian Text © 2014 I. I. Zakharov.
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Translated from Zhurnal Strukturnoi Khimii, Vol. 55, No. 4, pp. 631–640, July–August, 2014.
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Zakharov, I.I. Quantum chemical DFT calculations of the local structure of the hydrated electron and dielectron. J Struct Chem 55, 595–604 (2014). https://doi.org/10.1134/S0022476614040027
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DOI: https://doi.org/10.1134/S0022476614040027