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首页> 外文期刊>Journal of structural chemistry >QUANTUM CHEMICAL DFT CALCULATIONS OF THE LOCAL STRUCTURE OF THE HYDRATED ELECTRON AND DIELECTRON
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QUANTUM CHEMICAL DFT CALCULATIONS OF THE LOCAL STRUCTURE OF THE HYDRATED ELECTRON AND DIELECTRON

机译：水合电子和电介质局部结构的量子化学DFT计算

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摘要

The adiabatic bound state of an excess electron is calculated for a water cluster (H_2O)_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, ε = 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(H_2O)_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 (H_2O)_8~- cluster in the liquid phase (VBE = 1.70 eV) corresponds well to the absorption band maximum λ_(max) = 715 nm (VBE = 1.73 eV) in the optical spectrum of the hydrated electron e_(hydr)~-. Estimating the adiabatic binding energy (ABE) e_(hydr)~-in the (H_2O)_8~- cluster (ABE = 1.63 eV), we obtain good agreement with the experimental free energy of electron hydration ?G_(298)~0 (e_(hydr)~-) = 1.61 eV. The local model (H_2O)_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.
机译：使用扩展的6-311 ++ G（3df，3pd）基集的DFT-B3LYP方法，计算了气相中水簇（H_2O）_8〜-的过量电子的绝热结合态。对于液相，在可极化连续体模型（PCM）中针对超分子-连续体近似中的溶剂效应（水，ε= 78.38）进行计算。通过DFT-B3LYP计算得出的阴离子簇中过量电子的垂直键能（VBE）的值（VBE（H_2O）_8〜-= 0.59 eV）与从光电子光谱获得的0.44 eV的实验值非常吻合。气相。由PCM-B3LYP计算的液相中（H_2O）_8〜-簇的过量电子的VBE值（VBE = 1.70 eV）对应于最大吸收带λ_（max）= 715 nm（VBE = 1.73 eV） ）在水合电子e_（hydr）〜-的光谱中。估算（H_2O）_8〜-（ABE = 1.63 eV）团中的绝热结合能（ABE）e_（hydr）〜-，我们与电子水合实验的自由能？G_（298）〜0（ e_（水合物〜-）= 1.61 eV。在超分子-连续谱近似中考虑了水合双电子的局部模型（H_2O）_8〜（2-）。结果表明，水合电子和双电子具有相同的特征局部结构：分别为–O–H {↑} H–O–和–O–H {↑↓} H–O–。

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