Calculation of the ground and excited states of a mixed valence compound [Fe2(OH)3(NH3)6]2+: a class II or class III compound?
Calculation of the ground and excited states of a mixed valence compound [Fe2(OH)3(NH3)6]2+: a class II or class III compound?
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计算混合价化合物 [Fe2(OH)3(NH3)6]2 的基态和激发态：II 类或 III 类化合物？
DOI：
10.1021/ic034716h
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发表时间：
2004
影响因子：
4.6
通讯作者：
J. Daudey
中科院分区：
文献类型：
--
作者：
Yannick Carissan;J. Heully;Fabienne Alary;J. Daudey
用有效基团势（EGP）方法计算了混合价化合物[Fe_2（OH）_3（NH_3）_6]~（2+）的基态和激发态能量.这是第一次，对于一个系统一样大的复杂以上提出的地面和激发态的计算与自己的轨道，并在这样一个详细的方式研究。首先，通过比较在不同计算水平下明确处理NH3的计算来验证NH3 EGP。一旦得到验证，就计算出感兴趣的化合物的完整光谱，并与Barone等人以前的工作和广泛使用的自旋哈密顿量进行比较。观察到与这些预测方法的一些偏差。这使我们能够强调动态相关的重要性，这是没有明确包括在自旋哈密顿量。然后，振动的影响已被研究，通过计算的势能曲线时，移动的（OH）3平面。这项研究表明，我们的计算导致一个离域的化合物（III类），根据以前的实验数据预期。
The effective group potentials (EGP) approach has been successfully used for the computation of the ground and excited states energies of the mixed valence compound [Fe2(OH)3(NH3)6]2+. It is the first time that for a system as big as the complex presented above the ground and excited states are computed with their own orbitals and studied in such a detailed way. First of all, the NH3 EGP was validated by comparing calculations where NH3 was treated explicitly at different levels of calculations. Once the validation was obtained, the complete spectrum of the compound under interest was calculated and compared with results obtained in a previous work by Barone et al. and the spin Hamiltonian of widespread use. Some deviations from these predictive approaches were observed. This allowed us to emphasize the importance of the dynamic correlation which is not included explicitly in the spin Hamiltonian. Then, the influence of vibration has been studied by computing the potential energy curves obtained when moving the (OH)3 plane. This study shows that our calculations lead to a delocalized compound (class III) as expected according to former experimental data.