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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >RASPT2 Analysis of the F-(H2O)(n=1-7) and OH-(H2O)(n=1-7) CTTS States
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RASPT2 Analysis of the F-(H2O)(n=1-7) and OH-(H2O)(n=1-7) CTTS States

机译：F-（H2O）（n = 1-7）和OH-（H2O）（n = 1-7）CTTS状态的RASPT2分析

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摘要

We analyze the electronic structure of the lowest excited states of the F-(H2O)(n=1-7) and OH-(H2O)(n=1-7) anionic clusters in the framework of RASPT2 theory. At the ground-state geometry, these clusters can bind the excess electron in the first excited singlet and triplet states for n = 3 for F- and n = 2 for OH-. The geometry relaxation of the F-(H2O)(n=1-7) clusters in their lowest-energy triplet state produces two series of minima. A first series is made of a F radical weakly bound to a negatively charged water cluster to form F-(H2O)n(-). A second series associated with hydrogen transfer from a water molecule to the fluorine atom is built on a HF molecule and a OH radical bound to a negatively charged water cluster to form OH-HF-(H2O)(n-)(-)(1). This second series provides the lowest-energy isomers of F-(H2O)(n) for the excited state. These two series of minima are inherited from the neutral fluorine water cluster structure only weakly perturbed by the excess electron. They are similar to the OH-(H2O)(n) isomers obtained for the lowest-energy triplet state, which are also made of a neutral OH radical inserted in the water molecule network of a (H2O)n(-) cluster. For all of these clusters in the lowest-energy excited state, the excess electron is localized outside of the cluster near unbound hydrogen atoms. Its binding energy is well correlated to the electric dipole of the cluster, and a lower limit of 4.1 D is necessary to bind it to the cluster. The two series of F-(H2O)(n) isomers offer two very different routes for geminate recombination observed in water solutions. Our calculation suggests that the recombination takes place with the OH radical left after hydrogen transfer rather than with the F radical.
机译：在RASPT2理论的框架中，我们分析了F-（H2O）（n = 1-7）（n = 1-7）（n = 1-7）（n = 1-7）和OH-（H2O）（n = 1-7）的阴离子簇的电子结构。在地态几何形状中，这些簇可以在第一激发态单次的单次突出的单次和三重态状态中结合N＆ = 3，对于OH-的F＆Gt; = 2。在其最低能量三重态状态下的F-（H2O）（N = 1-7）簇的几何松弛产生了两种最小值。第一系列由与带负电荷的水簇弱束的F型弱，以形成F-（H2O）N（ - ）。与来自水分子的氢转移到氟原子相关的第二系列基于HF分子和与带负电荷的水簇结合的OH自由基，以形成OH-HF-（H2O）（N - ）（ - ）（1 ）。该第二系列为激发态提供了F-（H2O）（N）的最低能量异构体。这两个系列的最小值是从中性氟水簇结构继承，仅通过过量电子弱扰动。它们类似于用于最低能量三重态状态的OH-（H 2 O）（N）异构体，其也由插入于（H2O）N（ - ）N（ - ）簇的水分子网络中的中性OH基团制成。对于在最低能量激发状态下的所有这些簇，过量的电子将在未结合的氢原子附近的簇之外定位。其结合能量与簇的电偶极孔良好，并且需要下限4.1d以将其绑定到簇中。两种F-（H2O）（N）异构体为在水溶液中观察到的GEMINITE重组提供两个非常不同的路线。我们的计算表明，在氢转移之后的OH左侧发生重组而不是用F基团进行重组。

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