title: Theoretical calculation of polarizability isotope effects.
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.
authors.affiliation: Chemistry Program, Universidad de la Amazonia, Calle 17 Diagonal 17 - Carrera 3F, Florencia, Colombia.
authors.forename: Félix
authors.initials: F
authors.lastname: Moncada
authors.affiliation: Department of Chemistry, Universidad de Guadalajara, Blvd. Marcelino García Barragán 1421, Guadalajara Jal., CP, 44430, Mexico.
authors.forename: Roberto
authors.initials: R
authors.lastname: Flores-Moreno
authors.affiliation: Department of Chemistry, Universidad Nacional de Colombia, Av. Cra. 30 #45-03, Bogotá, Colombia. areyesv@unal.edu.co.
authors.forename: Andrés
authors.initials: A
authors.lastname: Reyes
keywords: Density functional theory; Isotope effect; Non-covalent interactions; Nuclear orbital; Polarizability