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<p>Superacids, defined as compounds exhibiting acidities stronger than sulfuric acid, are essential in catalysis, synthesis, and material chemistry. Yet the quantitative understanding of their <i>intrinsic</i> acidity remains challenging due to the complex interplay of charge delocalization, resonance, and solvation effects. In this work, we employ density-based reactivity theory to describe and predict the equilibrium acidities of two major families of superacids— comprising four representative series of nitrogen-centered and carbon-centered species—each comprising multiple molecular series with experimentally measured pKₐ values available in 1,2-dichloroethane. Descriptors derived from conceptual density functional theory, information-theoretic approach, and topological analysis at bond critical points were systematically evaluated. Strong linear correlations between calculated descriptors and experimental pKₐ values were observed for N-centered superacids, confirming the robustness of density-based quantities in capturing intrinsic acidity. In contrast, weaker correlations for C-centered analogues reveal the multifaceted origins of their superacidity. Multi-descriptor regression further improves quantitative agreement across all systems. These findings demonstrate that superacidity is an emergent, electron density associated phenomenon that can be rationalized and predicted within the density-based reactivity framework.</p>

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Quantifying superacidity with density-based reactivity theory

  • 期刊论文

  • 发表日期：

    2025年12月16日

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  • Yaqin Zheng,
  • Xinyue Zhao,
  • Lei Zeng,
  • Chunying Rong,
  • Shubin Liu

摘要

Superacids, defined as compounds exhibiting acidities stronger than sulfuric acid, are essential in catalysis, synthesis, and material chemistry. Yet the quantitative understanding of their intrinsic acidity remains challenging due to the complex interplay of charge delocalization, resonance, and solvation effects. In this work, we employ density-based reactivity theory to describe and predict the equilibrium acidities of two major families of superacids— comprising four representative series of nitrogen-centered and carbon-centered species—each comprising multiple molecular series with experimentally measured pKₐ values available in 1,2-dichloroethane. Descriptors derived from conceptual density functional theory, information-theoretic approach, and topological analysis at bond critical points were systematically evaluated. Strong linear correlations between calculated descriptors and experimental pKₐ values were observed for N-centered superacids, confirming the robustness of density-based quantities in capturing intrinsic acidity. In contrast, weaker correlations for C-centered analogues reveal the multifaceted origins of their superacidity. Multi-descriptor regression further improves quantitative agreement across all systems. These findings demonstrate that superacidity is an emergent, electron density associated phenomenon that can be rationalized and predicted within the density-based reactivity framework.