ArticleThe journal of physical chemistry. A2010
Steric, quantum, and electrostatic effects on S(N)2 reaction barriers in gas phase.
Article in The journal of physical chemistry. A, 2010. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 18 papers.
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18 citing papers in PubMed, 101 citations in OpenAlex.
- Information-Theoretic Perspectives on Chemical Problems: Recent Developments and Applications.Entropy (Basel, Switzerland) · 2026Review
- Molecular Rotors as Reactivity Probes: Predicting Electrophilicity from the Speed of Rotation.Angewandte Chemie (International ed. in English) · 2025Article
- Why are information-theoretic descriptors powerful predictors of atomic and molecular polarizabilities.Journal of molecular modeling · 2024Article
- A real space picture of the role of steric effects in SJournal of computational chemistry · 2022Article
- Revisiting the trapping of noble gases (He-Kr) by the triatomic HJournal of molecular modeling · 2022Article
- Molecular Interactions From the Density Functional Theory for Chemical Reactivity: The Interaction Energy Between Two-Reagents.Frontiers in chemistry · 2022Article
- Theoretical Study of O-CHACS omega · 2021Article
- Toward Understanding the Isomeric Stability of Fullerenes with Density Functional Theory and the Information-Theoretic Approach.ACS omega · 2018Article
- Investigation of net unidirectional ring shuttling in a chemically fueled [2]catenane.Journal of molecular modeling · 2018Article
- SCI: a robust and reliable density-based descriptor to determine multiple covalent bond orders.Journal of molecular modeling · 2018Article
- Stretching vibration is a spectator in nucleophilic substitution.Science advances · 2018Article
- Nucleophilic Substitution (SChemphyschem : a European journal of chemical physics and physical chemistry · 2018Review
- An interacting quantum atom study of model SJournal of computational chemistry · 2018Article
- Evaluating frontier orbital energy and HOMO/LUMO gap with descriptors from density functional reactivity theory.Journal of molecular modeling · 2017Article
- Using the general-purpose reactivity indicator: challenging examples.Journal of molecular modeling · 2016Article
- Influence of the leaving group on the dynamics of a gas-phase SN2 reaction.Nature chemistry · 2016Article
- Density functional studies on photophysical properties and chemical reactivities of the triarylboranes: effect of the constraint of planarity.Journal of molecular modeling · 2013Article
- Regioselectivity of Catechol O-Methyltransferase Confers Enhancement of Catalytic Activity.Chemical physics letters · 2011Article
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Authors and funding
3 authors at 3 institutions in 2 countries.
Funding
Abstract
Biomolecular nucleophilic substitution reactions, S(N)2, are fundamental and commonplace in chemistry. It is the well-documented experimental finding in the literature that vicinal substitution with bulkier groups near the reaction center significantly slows the reaction due to steric hindrance, but theoretical understanding in the quantitative manner about factors dictating the S(N)2 reaction barrier height is still controversial. In this work, employing the new quantification approach that we recently proposed for the steric effect from the density functional theory framework, we investigate the relative contribution of three independent effects-steric, electrostatic, and quantum-to the S(N)2 barrier heights in gas phase for substituted methyl halide systems, R(1)R(2)R(3)CX, reacting with the fluorine anion, where R(1), R(2), and R(3) denote substituting groups and X = F or Cl. We found that in accordance with the experimental finding, for these systems, the steric effect dominates the transition state barrier, contributing positively to barrier heights, but this contribution is largely compensated by the negative, stabilizing contribution from the quantum effect due to the exchange-correlation interactions. Moreover, we find that it is the component from the electrostatic effect that is linearly correlated with the S(N)2 barrier height for the systems investigated in the present study. In addition, we compared our approach with the conventional method of energy decomposition in density functional theory as well as examined the steric effect from the wave function theory for these systems via natural bond orbital analysis.
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