对环状 H2O、H2S 和 H2O-H2S 簇中多质子转移的能量、几何、机械和动力学方面的量子化学研究

IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL International Journal of Quantum Chemistry Pub Date : 2024-07-05 DOI:10.1002/qua.27442
Monu, Binod Kumar Oram, Biman Bandyopadhyay
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摘要

我们以经济、精确的理论水平研究了从三聚体到五聚体的循环同源和混合 H2O-H2S 团簇中的多重质子转移。反应力和维伯格键指数分析表明,在所有同质簇中,质子转移过程几乎是同步进行的,而在混合簇中则是非同步进行的;质子转移总是由 SH 质子移动到以 H 键结合的 O 原子上开始的。质子转移的壁垒表现出复杂的模式,从均质 H2O 簇开始,当一个 H2O 被一个 H2S 分子取代时,壁垒降低,随后随着每次取代单调上升,在纯 H2S 簇中壁垒最高。最后,还研究了能量和机理调节对质子转移动力学的影响。
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A quantum chemical investigation of energetic, geometric, mechanistic, and kinetic aspects of multiple proton transfer in cyclic H2O, H2S, and H2O-H2S clusters

Multiple proton transfers in cyclic homogenous and mixed H2O-H2S clusters from trimers to pentamers have been investigated at an affordable and accurate level of theory. Reaction force and Wiberg bond index analyses showed the process to be nearly synchronous in all the homogenous clusters, while asynchronous in the mixed clusters; always initiated by movement of the SH protons to the H-bonded O atoms. The barriers for proton transfers exhibited a complex pattern, decreasing initially from the homogeneous H2O cluster upon replacement of one H2O by an H2S moiety and subsequently rising monotonically with each subsequent replacement(s) to becoming highest in pure H2S clusters. Finally, the impact of the energetic and mechanistic modulations on the proton transfer kinetics has been studied.

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来源期刊
International Journal of Quantum Chemistry
International Journal of Quantum Chemistry 化学-数学跨学科应用
CiteScore
4.70
自引率
4.50%
发文量
185
审稿时长
2 months
期刊介绍: Since its first formulation quantum chemistry has provided the conceptual and terminological framework necessary to understand atoms, molecules and the condensed matter. Over the past decades synergistic advances in the methodological developments, software and hardware have transformed quantum chemistry in a truly interdisciplinary science that has expanded beyond its traditional core of molecular sciences to fields as diverse as chemistry and catalysis, biophysics, nanotechnology and material science.
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