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Related Experiment Videos

Computer simulations of organic reactions in solution.

W L Jorgensen, J Chandrasekhar, J K Buckner

    Annals of the New York Academy of Sciences
    |January 1, 1986
    PubMed
    Summary

    Solvent effects significantly alter chemical reaction pathways. Hydration, for instance, increases activation barriers by changing hydrogen bond strengths, impacting reactions like SN2 and addition reactions.

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    Area of Science:

    • Computational chemistry
    • Physical chemistry
    • Chemical kinetics

    Background:

    • Understanding reaction mechanisms in different environments is crucial for chemical synthesis and biological processes.
    • Solvent effects, particularly solvation, play a significant role in modulating reaction energetics and kinetics.

    Purpose of the Study:

    • To investigate the influence of solvent environments (gas phase, aqueous solution, liquid DMF) on the energy profiles of chemical reactions.
    • To elucidate the role of hydrogen bonding in mediating solvent effects on reaction barriers.

    Main Methods:

    • Application of quantum and statistical mechanics to determine reaction energy profiles.
    • Utilizing ab initio 6-31 + G* calculations for electronic structure analysis.
    • Comparison of computed results with experimental free energies of activation.

    Main Results:

    • The SN2 reaction (Cl- + CH3Cl) exhibits a double-well profile in the gas phase, becoming unimodal with a higher barrier in aqueous solution.
    • The reaction profile in DMF is intermediate, with ion-dipole complexes remaining as free energy minima.
    • The addition reaction (OH- + H2C=O) proceeds without activation in the gas phase but gains a substantial barrier upon hydration.

    Conclusions:

    • Hydration significantly increases activation barriers for both studied reactions.
    • The primary cause of hydration-induced activation barriers is the alteration of solute-water hydrogen bond strengths, not just their number.
    • Computational methods provide accurate predictions of experimental activation energies, validating the theoretical approach.

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