Quantum chemical DFT calculations of the local structure of the hydrated electron and dielectron
| Autor: | I. I. Zakharov |
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| Rok vydání: | 2014 |
| Předmět: | |
| Zdroj: | Journal of Structural Chemistry. 55:595-604 |
| ISSN: | 1573-8779 0022-4766 |
| DOI: | 10.1134/s0022476614040027 |
| Popis: | 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 hydr t- in the (H2O) 8 − cluster (ABE = 1.63 eV), we obtain good agreement with the experimental free energy of electron hydration ΔG 298 0 (e hydr − ) = 1.61 eV. The local model (H2O) 8 2− 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. |
| Databáze: | OpenAIRE |
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