Whynot Daniel C M, Corbeil Christopher R, Mercer Darren J W, Pye Cory C
Department of Chemistry, Saint Mary's University, 923 Robie Street, Halifax, NS B3H 3C3, Canada.
Molecules. 2025 Jul 27;30(15):3147. doi: 10.3390/molecules30153147.
The determination of multiple energy minima on complex potential energy surfaces is challenging. A systematic desymmetrization procedure was employed to find stationary points on the copper(I) + chloride + water potential energy surface using HF, MP2, and B3LYP methods in conjunction with the 6-31G*, 6-31+G*, and 6-311+G* basis sets. Comparison with experimental results demonstrated that the speciation of copper(I) in the presence of chloride and water may be formulated as [CuCl(HO)], [CuCl], and [CuCl]. Our results indicate that the combination of the MP2 method along with basis sets containing diffuse functions gives excellent agreement with experimental Cu-Cl distances and vibrational frequencies. Poorer results were obtained at the HF levels and/or using the 6-31G* basis set.
确定复杂势能面上的多个能量极小值具有挑战性。采用了一种系统的去对称化程序，使用HF、MP2和B3LYP方法并结合6-31G*、6-31+G和6-311+G基组，在铜(I)+氯+水的势能面上寻找驻点。与实验结果的比较表明，在有氯和水存在的情况下，铜(I)的物种形成可表示为[CuCl(HO)]、[CuCl]和[CuCl]。我们的结果表明，MP2方法与包含弥散函数的基组相结合，能与实验得到的铜-氯距离和振动频率取得极好的一致性。在HF水平和/或使用6-31G*基组时得到的结果较差。
