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Isotopic Effects on Covalent Bond Confined in a Penetrable Sphere

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Departamento de Física, Facultad de Ciencias, Universidad de Córdoba, Campus de Rabanales, Edif. C2, E-14071 Córdoba, Spain
Université Paris Sud 11, CNRS, Institut des Sciences Moleculaires d’Orsay-ISMO (UMR 8214), 91405 Orsay Cedex, France
Cite this: J. Phys. Chem. B 2015, 119, 45, 14364–14372
Publication Date (Web):October 20, 2015
https://doi.org/10.1021/acs.jpcb.5b06758
Copyright © 2015 American Chemical Society

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    Abstract

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    A model of confinement of the covalent bond by a finite potential beyond the Born–Oppenheimer approximation is presented. A two-electron molecule is located at the center of a penetrable spherical cavity. The Schrödinger equation has been solved by using the diffusion Monte Carlo method. Total energies, internuclear distances, and vibrational frequencies of the confined molecular system have been obtained. Even for confining potentials of a few electronvolts, a noticeable increase in the bond energy and the nuclear vibrational frequency is observed, and the internuclear distance is lowered. The gap between the zero point energy of different molecular isotopes increases with confinement. The confinement of the electron pair might play a role in chemical reactivity, providing an alternative explanation for the tunnel effect, when large values of primary kinetic isotopic effect are observed. The Swain–Schaad relation is still verified when confinement changes the zero point energy. A semiquantitative illustration is proposed using the data relative to an hydrogen transfer involving a C–H cleavage catalyzed by the bovine serum amine oxidase. Changes on the confining conditions, corresponding to a confinement/deconfinement process, result in a significant decrease in the activation energy of the chemical transformation. It is proposed that confinement/deconfinement of the electron-pair bonding by external electrostatic forces inside the active pocket of an enzyme could be one of the basic mechanisms of the enzyme catalysis.

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    Cited By

    This article is cited by 15 publications.

    1. Natalia N. Breslavskaya, Anatoly L. Buchachenko. Isotope Effects Induced by Molecular Compression. The Journal of Physical Chemistry A 2020, 124 (31) , 6352-6355. https://doi.org/10.1021/acs.jpca.0c05567
    2. E. M. Pliss, A. L. Buchachenko. Nanoscale Confinement As a Means to Control Single Molecules. Russian Journal of Physical Chemistry A 2023, 97 (14) , 3201-3211. https://doi.org/10.1134/S0036024424030208
    3. Claude Le Sech. Changes induced in a covalent bond confined in a structured cavity. Chemical Physics Letters 2022, 791 , 139396. https://doi.org/10.1016/j.cplett.2022.139396
    4. A. L. Buchachenko. Compressed Molecules and Enzymes. Russian Journal of Physical Chemistry B 2022, 16 (1) , 9-17. https://doi.org/10.1134/S1990793122010031
    5. F. Arias de Saavedra, E. Buendía, F.J. Gálvez. The confined Be atom by soft potentials of Gaussian type. Chemical Physics Letters 2021, 763 , 138197. https://doi.org/10.1016/j.cplett.2020.138197
    6. A. A. Elkina, E. N. Tumaev, A. A. Basov, A. V. Moiseev, V. V. Malyshko, E. V. Barisheva, A. V. Churkina, S. S. Dzhimak. The Mechanisms of the Interaction of Stable Isotopes with Biological Objects in the Presence of an Uncompensated Neutron in Chemical Bonds. Biophysics 2020, 65 (5) , 883-888. https://doi.org/10.1134/S0006350920050048
    7. Salvador A. Cruz, Diego Garrido-Aguirre. Confinement effects on the diatomic interaction potential. Radiation Effects and Defects in Solids 2020, 175 (1-2) , 202-217. https://doi.org/10.1080/10420150.2020.1718144
    8. Alexander Basov, Liliya Fedulova, Ekaterina Vasilevskaya, Stepan Dzhimak. Possible Mechanisms of Biological Effects Observed in Living Systems during 2H/1H Isotope Fractionation and Deuterium Interactions with Other Biogenic Isotopes. Molecules 2019, 24 (22) , 4101. https://doi.org/10.3390/molecules24224101
    9. Raymundo Hernández‐Esparza, Bruno Landeros‐Rivera, Rubicelia Vargas, Jorge Garza. Electron Density Analysis for the H2+ System Confined by Hard Walls: The Chemical Bond Under Extreme Conditions. Annalen der Physik 2019, 531 (7) https://doi.org/10.1002/andp.201800476
    10. A. Sarsa, J. M. Alcaraz-Pelegrina, C. Le Sech. Exclusion principle repulsion effects on the covalent bond beyond the Born–Oppenheimer approximation. Physical Chemistry Chemical Physics 2019, 21 (20) , 10411-10416. https://doi.org/10.1039/C9CP01063G
    11. Milagros F. Morcillo, José M. Alcaraz-Pelegrina, Antonio Sarsa. Ionization probability of the hydrogen atom suddenly released from confinement. International Journal of Quantum Chemistry 2018, 118 (12) , e25563. https://doi.org/10.1002/qua.25563
    12. Francisco J. Gálvez, Enrique Buendía, Antonio Sarsa. Confinement effects on the electronic structure of M-shell atoms: A study with explicitly correlated wave functions. International Journal of Quantum Chemistry 2017, 117 (19) , e25421. https://doi.org/10.1002/qua.25421
    13. Li Guang Jiao, Li Rong Zan, Yong Zhi Zhang, Yew Kam Ho. Benchmark values of S hannon entropy for spherically confined hydrogen atom. International Journal of Quantum Chemistry 2017, 117 (13) https://doi.org/10.1002/qua.25375
    14. A. Sarsa, J.M. Alcaraz-Pelegrina, C. Le Sech. The hydrogen atom confined by one and two hard cones. Physics Letters A 2017, 381 (8) , 780-786. https://doi.org/10.1016/j.physleta.2016.12.047
    15. A Sarsa, E Buendía, F J Gálvez. Multi-configurational explicitly correlated wave functions for the study of confined many electron atoms. Journal of Physics B: Atomic, Molecular and Optical Physics 2016, 49 (14) , 145003. https://doi.org/10.1088/0953-4075/49/14/145003

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