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<p>The development of the theoretical approach based on the concept of “Transition State Shape Selectivity” is proposed, which allows screening of porous materials for their ability to increase the reaction selectivity. The key features of this approach are modeling of the interactions of transition state (TS) with a cavity and using the frozen TS structure as a probe. The consequences of replacing semi-empirical methods with molecular mechanics (MM) in this approach of catalytic activity assessment are considered. Using zeolite clusters with full channels for a list of frameworks with various pore sizes (namely ANA, NAT, TON, MTW, LOS, EUO, MEL, MEI and KFI) as a screening set, PM6-D3H4 was selected as the most adequate method for this type of modeling. Using TSs of the Prins reaction as probes, it was shown that the energy of TS placement in a cavity nonlinearly depends on the channel diameter and reaches a minimum at a certain optimal diameter, which depends on the TS size. Using PM6-D3H4 and AM1 methods, it is shown that searching for the TS structure directly in the zeolite pore only slightly changes the TS geometrical and electronic parameters relative to the TS structure, which was optimized in isolation. Therefore, using frozen TS structures seems justified, and determining only the optimal TS placement in the cavity is sufficient for adequate screening results. Using PM6-D3H4 instead of MM allows one, e.g., to correctly evaluate the influence of elemental exchanges in zeolite frameworks, such as the changes in the Al:Si ratio.</p> Graphical Abstract <p></p>

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Quantum Chemical Semi-empirical Approach in Transition-State-Shape-Selectivity-Based Catalytic Activity Prediction: Application to Zeolites

  • 期刊论文

  • 发表日期：

    2025年12月6日

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  • Ivan V. Vakulin,
  • Denis Rakhmanov,
  • Rifkat F. Talipov,
  • Rufina A. Zilberg,
  • Guzalia R. Talipova

摘要

The development of the theoretical approach based on the concept of “Transition State Shape Selectivity” is proposed, which allows screening of porous materials for their ability to increase the reaction selectivity. The key features of this approach are modeling of the interactions of transition state (TS) with a cavity and using the frozen TS structure as a probe. The consequences of replacing semi-empirical methods with molecular mechanics (MM) in this approach of catalytic activity assessment are considered. Using zeolite clusters with full channels for a list of frameworks with various pore sizes (namely ANA, NAT, TON, MTW, LOS, EUO, MEL, MEI and KFI) as a screening set, PM6-D3H4 was selected as the most adequate method for this type of modeling. Using TSs of the Prins reaction as probes, it was shown that the energy of TS placement in a cavity nonlinearly depends on the channel diameter and reaches a minimum at a certain optimal diameter, which depends on the TS size. Using PM6-D3H4 and AM1 methods, it is shown that searching for the TS structure directly in the zeolite pore only slightly changes the TS geometrical and electronic parameters relative to the TS structure, which was optimized in isolation. Therefore, using frozen TS structures seems justified, and determining only the optimal TS placement in the cavity is sufficient for adequate screening results. Using PM6-D3H4 instead of MM allows one, e.g., to correctly evaluate the influence of elemental exchanges in zeolite frameworks, such as the changes in the Al:Si ratio.

Graphical Abstract