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用量子化学密度泛函理论(DFT),分别在B3PW91/Lan12DZ和B3PW91/6-31G的计算水平上,优化Ni离子水、羟基配合物几种可能的构型。分析比较了Ni(OH)_6~(4-)和Ni(H_2O)_6~(2+)化合物的几何参数、能量、前线轨道、电荷分布及振动频率。结果:优化的健参数中,Ni-O键长与文献的实验数据较一致。Ni(H_2O)_6~(2+)比Ni(OH)_6~(4-)更稳定,但后者更易吸引带正电荷的阳离子。从前线轨道图也可以看出,Ni(OH)_6~(4-)最高占据轨道HOMO主要集中于配体O上,易于向受体流动提供电子与带正电荷的阳离子结合。振动分析的Ni(H_2O)_6~(2+)和Ni(OH)_6~(4-)的红外吸收峰与实验值相一致。
Quantum chemical density functional theory (DFT) is used to optimize the possible configurations of Ni ionized water and hydroxyl complex on the B3PW91 / Lan12DZ and B3PW91 / 6-31G computational levels, respectively. The geometrical parameters, energy, frontier orbital, charge distribution and vibration frequency of Ni (OH) 6 ~ (4-) and Ni (H_2O) 6 ~ (2+) compounds were analyzed and compared. Results: In the optimized parameters, Ni-O bond length is consistent with the experimental data in the literature. Ni (H_2O) _6 ~ (2+) is more stable than Ni (OH) _6 ~ (4-), but the latter is more attractive to positively charged cations. It can also be seen from the frontier orbital diagram that the highest occupied orbital HOMO of Ni (OH) 6 ~ (4-) is mainly concentrated on the ligand O, and it is easy to provide electrons to the acceptors to combine with positively charged cations. The infrared absorption peaks of Ni (H_2O) _6 ~ (2+) and Ni (OH) _6 ~ (4-) are consistent with the experimental data.