Faculty of Chemistry, University of Wrocław, ul. F. Joliot-Curie 14, 50-383 Wrocław, Poland.
Molecules. 2022 Feb 11;27(4):1225. doi: 10.3390/molecules27041225.
n-Octanol is the object of experimental and theoretical study of spectroscopic signatures and intermolecular interactions. The FTIR measurements were carried out at 293 K for n-octanol and its deuterated form. Special attention was paid to the vibrational features associated with the O-H stretching and the isotope effect. Density Functional Theory (DFT) in its classical formulations was applied to develop static models describing intermolecular hydrogen bond (HB) and isotope effect in the gas phase and using solvent reaction field reproduced by Polarizable Continuum Model (PCM). The Atoms in Molecules (AIM) theory enabled electronic structure and molecular topology study. The Symmetry-Adapted Perturbation Theory (SAPT) was used for energy decomposition in the dimers of n-octanol. Finally, time-evolution methods, namely classical molecular dynamics (MD) and Car-Parrinello Molecular Dynamics (CPMD) were employed to shed light onto dynamical nature of liquid n-octanol with emphasis put on metric and vibrational features. As a reference, CPMD gas phase results were applied. Nuclear quantum effects were included using Path Integral Molecular Dynamics (PIMD) and a posteriori method by solving vibrational Schrödinger equation. The latter applied procedure allowed to study the deuterium isotope effect.
辛醇是实验和理论研究光谱特征和分子间相互作用的对象。在 293 K 下对辛醇及其氘代形式进行了傅里叶变换红外（FTIR）测量。特别关注与 O-H 伸缩振动和同位素效应相关的振动特征。应用经典形式的密度泛函理论（DFT）开发了静态模型，以描述气相中的分子间氢键（HB）和同位素效应，并使用极化连续体模型（PCM）再现溶剂反应场。分子中的原子（AIM）理论能够进行电子结构和分子拓扑研究。对称自适应微扰理论（SAPT）用于二聚体的能量分解。最后，采用时间演化方法，即经典分子动力学（MD）和 Car-Parrinello 分子动力学（CPMD），研究液态辛醇的动力学性质，重点关注度量和振动特征。作为参考，应用了 CPMD 气相结果。使用路径积分分子动力学（PIMD）和通过求解振动薛定谔方程的后验方法包含核量子效应。后一种应用程序允许研究氘同位素效应。
