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Theoretical calculation of polarizability isotope effects

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Abstract

We propose a scheme to estimate hydrogen isotope effects on molecular polarizabilities. This approach combines the any-particle molecular orbital method, in which both electrons and H/D nuclei are described as quantum waves, with the auxiliary density perturbation theory, to calculate analytically the polarizability tensor. We assess the performance of method by calculating the polarizability isotope effect for 20 molecules. A good correlation between theoretical and experimental data is found. Further analysis of the results reveals that the change in the polarizability of a X-H bond upon deuteration decreases as the electronegativity of X increases. Our investigation also reveals that the molecular polarizability isotope effect presents an additive character. Therefore, it can be computed by counting the number of deuterated bonds in the molecule.

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Acknowledgments

We gratefully acknowledge the support of Universidad Nacional de Colombia and Universidad de la Amazonia.

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Authors and Affiliations

  1. Chemistry Program, Universidad de la Amazonia, Calle 17 Diagonal 17 - Carrera 3F, Florencia, Colombia

    Félix Moncada

  2. Department of Chemistry, Universidad de Guadalajara, Blvd. Marcelino García Barragán 1421, Guadalajara Jal., CP, 44430, Mexico

    Roberto Flores-Moreno

  3. Department of Chemistry, Universidad Nacional de Colombia, Av. Cra. 30 #45-03, Bogotá, Colombia

    Andrés Reyes

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  1. Félix Moncada
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  2. Roberto Flores-Moreno
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  3. Andrés Reyes
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Correspondence to Andrés Reyes.

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This paper belongs to Topical Collection Festschrift in Honor of Henry Chermette

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Moncada, F., Flores-Moreno, R. & Reyes, A. Theoretical calculation of polarizability isotope effects. J Mol Model 23, 90 (2017). https://doi.org/10.1007/s00894-017-3236-9

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