去局域化水和氟化物对水合氟离子中电子脱离的狄森轨道的贡献。

Delocalized water and fluoride contributions to Dyson orbitals for electron detachment from the hydrated fluoride anion.

机构信息

Instituto de Física, Universidade de São Paulo, CP 66318, 05314-970, São Paulo, SP, Brazil.

出版信息

J Chem Phys. 2010 Jun 7;132(21):214507. doi: 10.1063/1.3431081.

PMID:20528031

Abstract

The experimental vertical electron detachment energy (VEDE) of aqueous fluoride, [F(-)(H(2)O)], is approximately 9.8 eV, but spectral assignment is complicated by interference between F(-) 2p and H(2)O 1b(1) orbitals. The electronic structure of [F(-)(H(2)O)] is analyzed with Monte Carlo and ab initio quantum-mechanical calculations. Electron-propagator calculations in the partial third-order approximation yield a VEDE of 9.4 eV. None of the Dyson orbitals corresponding to valence VEDEs consists primarily of F 2p functions. These results and ground-state atomic charges indicate that the final, neutral state is more appropriately described as [F(-)(H(2)O)(+)] than as [F(H(2)O)].

摘要

实验得出的水合氟离子（[F(-)(H(2)O)]）的垂直电子亲合能（VEDE）约为 9.8eV，但由于 F(-) 2p 和 H(2)O 1b(1)轨道之间的干扰，光谱分配较为复杂。采用蒙特卡罗和从头算量子力学计算方法对[F(-)(H(2)O)]的电子结构进行了分析。部分三阶近似的电子传播子计算得出的 VEDE 为 9.4eV。与价 VEDE 对应的狄森轨道都没有主要由 F 2p 函数组成。这些结果和基态原子电荷表明，最终的中性态更适合描述为[F(-)(H(2)O)(+)]，而不是[F(H(2)O)]。