部分Hessian振动分析：蒸气压同位素效应及其与非共价相互作用的关系
Partial Hessian vibrational analysis: vapour pressure isotope effects and their relation with non-covalent interactions
摘要：
在这项研究中，平衡同位素效应（EIEs）的蒸发到几个有机溶剂（溴苯，二溴甲烷，乙醇，甲醇，三氯甲烷）在纯相估计采用Kohn-Sham密度泛函理论（KS-DFT）以及全Hessian振动分析（FHVA）和部分Hessian振动分析（PHVA）。FHVA和PHVA都能定性预测化合物EIE。弱相互作用系统（溴苯，二溴甲烷，三氯甲烷）显示相同的EIE值，FHVA和PHVA。而对于强相互作用的系统（乙醇和甲醇），PHVA估计EIE略小于FHVA。通过采用自适应微扰理论（SAPT）以及独立梯度模型（IGM），它是可能的，以建立化合物相互作用能的最小变化如何影响碳和溴EIEs估计在二溴甲烷。此外，SAPT和IGM揭示了在乙醇中，显然微不足道的分子间相互作用如何对碳位置特异性同位素效应产生巨大影响，这突出了溶剂效应对强相互作用化合物的重要性。所提出的结果具有重要的意义，正确理解和表征的作用，非共价相互作用的同位素效应的预测，以及提供一个强大的测试PHVA的EIEs的预测。
英文摘要：
In this study equilibrium isotope effects (EIEs) on evaporation to several organic solvents (bromobenzene, dibromomethane, ethanol, methanol, and trichloromethane) in the pure phase are estimated employing Kohn-Sham Density functional theory (KS-DFT) along with full Hessian vibrational analysis (FHVA) and partial Hessian vibrational analysis (PHVA). Both FHVA and PHVA qualitatively predict compounds EIEs. Weakly interacting systems (bromobenzene, dibromomethane, and trichloromethane) display identical EIE values for both, FHVA and PHVA. Whereas for strongly interacting systems (ethanol and methanol), PHVA estimates slightly smaller EIE compared to FHVA. By employing the symmetry-adapted perturbation theory (SAPT) along with independent gradient model (IGM), it was possible to establish how minimal changes in compounds interaction energy affected carbon and bromine EIEs estimation in dibromomethane. Moreover, SAPT and IGM revealed how in ethanol, apparently insignificant intermolecular interactions possessed an enormous impact in carbon position specific isotope effects, which highlight the importance of solvent effects for strongly interacting compounds. The presented results have important implications for correctly comprehending and characterising the role of non-covalent interactions in the prediction of isotope effects, as well as providing a robust test to PHVA for the prediction of EIEs.
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