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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Hydrates of Cu~(2+) and CuCl~+ in dilute aqueous solution: A density functional theory and polarized continuum model investigation
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Hydrates of Cu~(2+) and CuCl~+ in dilute aqueous solution: A density functional theory and polarized continuum model investigation

机译：稀水溶液中Cu〜（2+）和CuCl〜+的水合物：密度泛函理论和极化连续模型研究

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摘要

In this work, structures, and properties of Cu~(2+) and CuCl ~+ hydrates in the gas and aqueous phases have been investigated using the B3LYP method. Contact ion pair (CIP) and solvent-shared ion pair (SSIP) were both taken into account for CuCl~+ hydrates. Our calculations show that [Cu(H_2O)_n]~(2+) clusters favor a very open four-coordinated structure for n = 5-12 in the gas phase, while a five-coordinated conformer is favored for n ≥ 8 in the aqueous phase. An approximate complete solvation shell of Cu~(2+) in the aqueous phase needs more than 12 water molecules, while that of CuCl~+ in the aqueous phase needs only about eight water molecules. For [CuCl(H _2O)_n]~+ clusters, the most stable structure is a four-coordinated CIP conformer for n = 4-7 in the gas phase and a five-coordinated CIP conformer for n = 8-10 in the aqueous phase. However, the five-coordinated CIP/h conformer (CIP conformer that the axial chloride atom tends to dissociate) of [CuCl(H_2O)_n]~+ clusters becomes more favorable as n increases to 11. As the hydration process proceeds, the charges on the copper atom of [Cu(H_2O)_n]~(2+) clusters decrease, while those of [CuCl(H_2O)_n]~+ clusters increase (probably due to the dissociation of Cl~-). The d-d electron transition and partial charge transition band around 160 nm of the five-coordinated conformer of [Cu(H_2O)_n]~(2+) clusters and those bands (～170 and ～160 nm) of SSIP or five-coordinated CIP/h conformers of [CuCl(H_2O)_n]~+ clusters are coincident with the absorption of [Cu]~(2+)(aq) species (～180 nm) resolved from the spectra obtained in trace CuCl_2 (ca. 10 ~(-5) mol·kg~(-1)) + LiCl (0-18 mol·kg ~(-1)) aqueous solution, while those of five-coordinated CIP conformers of [CuCl(H_2O)_n]~+ clusters (n = 8 and 9) around 261 and 247 nm correspond to the absorption of [CuCl]~+(aq) species (～250 nm). Our calculated electronic spectra indicate that the typical peak of copper(II)-chloride complexes changes from 180 to 250 nm, and 275 nm, as the process of Cl~- coordination. For [Cu]~(2+)(aq), [CuCl] ~+(aq), and [CuCl_2]~0(aq) species, the central Cu(II) atom prefers five-coordination.
机译：在这项工作中，已使用B3LYP方法研究了气相和水相中Cu〜（2+）和CuCl〜+水合物的结构和性质。 CuCl〜+水合物考虑了接触离子对（CIP）和溶剂共享离子对（SSIP）。我们的计算表明，[Cu（H_2O）_n]〜（2+）团簇在气相中n = 5-12时倾向于非常开放的四配位结构，而当n≥8时则倾向于五配位构型。水相。 Cu〜（2+）在水相中的近似完整溶剂化壳需要12个以上的水分子，而CuCl〜+在水相中的溶剂化壳仅需要约8个水分子。对于[CuCl（H _2O）_n]〜+团簇，最稳定的结构是气相中n = 4-7的四配位CIP构象异构体和水溶液中n = 8-10的五配位CIP构象异构体。相。但是，当n增加到11时，[CuCl（H_2O）_n]〜+簇的五配位CIP / h构象异构体（轴向氯化物趋于解离的CIP构象异构体）变得更有利。随着水合过程的进行，电荷[Cu（H_2O）_n]〜（2+）团簇的铜原子的原子数减少，而[CuCl（H_2O）_n]〜+团簇的铜原子的原子数增加（可能是由于Cl〜-的解离）。 [Cu（H_2O）_n]〜（2+）团簇的五配位构象体在160 nm附近的dd电子跃迁和部分电荷跃迁带以及SSIP或五配位CIP的那些能带（〜170和〜160 nm） [CuCl（H_2O）_n]〜+团簇的/ h构象与从痕量CuCl_2（约10〜）解析得到的[Cu]〜（2 +）（aq）物种（〜180 nm）的吸收一致。 （-5）mol·kg〜（-1））+ LiCl（0-18 mol·kg〜（-1））水溶液，[CuCl（H_2O）_n]〜+簇五配位CIP构象的簇（n = 8和9）在261和247 nm附近对应于[CuCl]〜+（aq）物种（〜250 nm）的吸收。我们计算出的电子光谱表明，随着Cl〜-配位的过程，氯化铜（II）配合物的典型峰从180 nm改变为250 nm，而在275 nm改变。对于[Cu]〜（2 +）（aq），[CuCl]〜+（aq）和[CuCl_2]〜0（aq）而言，中心的Cu（II）原子更倾向于五配位。

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