Moncada Félix, Flores-Moreno Roberto, Reyes Andrés
Chemistry Program, Universidad de la Amazonia, Calle 17 Diagonal 17 - Carrera 3F, Florencia, Colombia.
Department of Chemistry, Universidad de Guadalajara, Blvd. Marcelino García Barragán 1421, Guadalajara Jal., CP, 44430, Mexico.
J Mol Model. 2017 Mar;23(3):90. doi: 10.1007/s00894-017-3236-9. Epub 2017 Feb 22.
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.
我们提出了一种估算氢同位素对分子极化率影响的方案。该方法将把电子和H/D核都描述为量子波的任意粒子分子轨道方法与辅助密度微扰理论相结合，以解析计算极化率张量。我们通过计算20种分子的极化率同位素效应来评估该方法的性能。发现理论数据与实验数据之间具有良好的相关性。对结果的进一步分析表明，氘代后X-H键极化率的变化随着X电负性的增加而减小。我们的研究还表明，分子极化率同位素效应具有加和性。因此，可以通过计算分子中氘代键的数量来计算它。
