European Laboratory for Nonlinear Spectroscopy, Via Nello Carrara 1, 50019 Sesto Fiorentino, Italy.
J Chem Phys. 2012 Dec 28;137(24):244501. doi: 10.1063/1.4770499.
Hydrogen bond interactions strongly affect vibrational properties and frequencies, the most common consequence being a redshift of the stretching vibration involved; there are, however, few exceptions to this general trend. In previous works, we have proved the effectiveness of ab initio simulations combined with wavelet analysis to investigate these effects and put them into relation to structural environment. In this work, we investigate the hydrogen bond effects on the structural and vibrational properties of 1,3-propanediol in acetonitrile by a combined experimental and computational approach. We explain the appearance of two spectral components in the O-H stretching band on the basis of intra- and intermolecular hydrogen bond interactions. We also elucidate the blueshift of the C≡N stretching band as due to a hydrogen bond interaction between the glycol and acetonitrile that modify the electron density distribution inside the CN group. This effect is well reproduced by ab initio molecular dynamics simulations and density functional calculations reported in this work.
氢键相互作用强烈影响振动特性和频率，最常见的结果是涉及的伸缩振动红移；然而，这种一般趋势也有少数例外。在以前的工作中，我们已经证明了从头算模拟结合小波分析来研究这些效应并将它们与结构环境联系起来的有效性。在这项工作中，我们通过实验和计算相结合的方法研究了 1,3-丙二醇在乙腈中的氢键对结构和振动特性的影响。我们根据分子内和分子间氢键相互作用解释了 O-H 伸缩带中两个谱分量的出现。我们还阐明了 C≡N 伸缩带的蓝移是由于二醇和乙腈之间的氢键相互作用，该相互作用改变了 CN 基团内部的电子密度分布。这项工作中报告的从头算分子动力学模拟和密度泛函计算很好地再现了这种效应。
