KLGHEI of Environment and Energy Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, China.
J Mol Model. 2013 Mar;19(3):1273-83. doi: 10.1007/s00894-012-1659-x. Epub 2012 Nov 23.
A combined and sequential use of quantum mechanical (QM) calculations and classical molecular dynamics (MD) simulations was made to investigate the σ and π types of hydrogen bond (HB) in benzene-water and pyrrole-water as clusters and as their liquid mixture, respectively. This paper aims at analyzing similarities and differences of these HBs resulted from QM and MD on an equal footing. Based on the optimized geometry at ωb97xD/aug-cc-pVTZ level of theory, the nature and property of σ and π types of HBs are unveiled by means of atoms in molecules (AIM), natural bond orbital (NBO) and energy decomposition analysis (EDA). In light of the above findings, MD simulation with OPLS-AA and SPC model was applied to study the liquid mixture at different temperatures. The MD results further characterize the behavior and structural properties of σ and π types HBs, which are somewhat different but reasonable for the clusters by QM. Finally, we provide a reasonable explanation for the different solubility between benzene/water and pyrrole/water.
采用量子力学（QM）计算和经典分子动力学（MD）模拟的组合和顺序方法，分别研究了苯-水和吡咯-水作为簇以及其液态混合物中的σ和π型氢键（HB）。本文旨在平等地分析QM 和 MD 得出的这些氢键的相似点和不同点。基于ωb97xD/aug-cc-pVTZ 理论水平的优化几何形状，通过分子中的原子（AIM）、自然键轨道（NBO）和能量分解分析（EDA）揭示了σ和π型 HB 的性质和性质。根据上述发现，采用 OPLS-AA 和 SPC 模型的 MD 模拟应用于不同温度下的液态混合物研究。MD 结果进一步描述了σ和π型 HB 的行为和结构性质，这些性质对于 QM 的簇有些不同，但却是合理的。最后，我们对苯/水和吡咯/水之间不同的溶解度提供了合理的解释。
