Theoretical study on the dissociation of HCl-(H2O)1–30 and HNO3-(H2O)1–30 clusters

IF 3 3区化学 Q3 CHEMISTRY, PHYSICAL

Computational and Theoretical Chemistry Pub Date : 2025-09-30 DOI:10.1016/j.comptc.2025.115518

Christian Tshikala Mukeba , Okuma Emile Kasende , Mireille K. Bilonda , Hoeil Chung , Jules Tshishimbi Muya

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Abstract

HCl-(H₂O)_n and HNO₃-(H₂O)_n clusters are HCl complexes and HNO₃ complexes constituted by small assemblies of n water molecules forming hydrogen bond network with HCl and HNO₃, respectively. Herein, a comparative study on HCl-(H₂O)_n and HNO₃-(H₂O)_n (n ≤ 29) is performed at the B3LYP-D3, ωB97XD, M06-2x, and MP2 levels with the 6–31 + G(d,p) basis set, focusing on hydrogen bonding interactions, relative stabilities, cooperativity energies, NBO charge transfer and vibration of H₃O⁺. The results show that water clusters tend to stabilize more HNO₃ than HCl based on computed binding energies and cooperativity energies. At least four and five water molecules are required for a total dissociation of HCl and HNO₃, respectively. Comparison between endohedral and exohedral clusters HCl-(H₂O)_n and HNO₃-(H₂O)_n (n = 19–20, 27–29) shows that chloride and nitrate are more stabilized inside the cage, unlike H₃O⁺ which prefers laying on the cluster surface. The third overtones of OH mode of H₃O⁺ in HCl-water and HNO₃-water large clusters are found to be in good agreement with experiments laying around 9000–7700 cm⁻¹.

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HCl-(H2O) 1-30和HNO3-(H2O) 1-30簇解离的理论研究

HCl-(H2O)n和HNO3-(H2O)n簇分别是由n个水分子的小集合与HCl和HNO3形成氢键网络而构成的HCl配合物和HNO3配合物。本文对HCl-(H2O)n和HNO3-(H2O)n （n≤29）在B3LYP-D3、ωB97XD、M06-2x和MP2能级(6-31 + G（d,p）基集上进行了对比研究，重点研究了h30o +的氢键相互作用、相对稳定性、协同能、NBO电荷转移和振动。结果表明，基于结合能和协同能的计算，水团簇对HNO3的稳定性高于HCl。要完全解离HCl和HNO3，至少需要4个和5个水分子。HCl-(H2O)n和HNO3-(H2O)n （n = 19 - 20,27 - 29）在笼内和笼外簇的比较表明，氯化物和硝酸盐在笼内更稳定，而h30o +更倾向于在簇表面。在hcl -水和hno3 -水大团簇中，h30 + OH模式的第三泛音与实验结果一致，分布在9000 ~ 7700 cm−1附近。

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来源期刊

Computational and Theoretical Chemistry CHEMISTRY, PHYSICAL-

CiteScore

4.20

自引率

10.70%

发文量

331

审稿时长

31 days

期刊介绍： Computational and Theoretical Chemistry publishes high quality, original reports of significance in computational and theoretical chemistry including those that deal with problems of structure, properties, energetics, weak interactions, reaction mechanisms, catalysis, and reaction rates involving atoms, molecules, clusters, surfaces, and bulk matter.