Tupikina Elena Yu, Tokhadze Konstantin G, Karpov Valerii V, Denisov Gleb S, Tolstoy Peter M
Institute of Chemistry, St. Petersburg State University, 26 Universitetskii pr., Petergof, St. Petersburg 198504, Russia.
Department of Physics, St. Petersburg State University, 3 Uljanoyskaya str., Petergof, St. Petersburg 198504, Russia.
Spectrochim Acta A Mol Biomol Spectrosc. 2020 Nov 5;241:118677. doi: 10.1016/j.saa.2020.118677. Epub 2020 Jul 3.
In this work applicability of proton donor group stretching vibration force constants k and intermolecular stretching force constants k for evaluations of hydrogen bond strength and geometry are discussed. For a set of 30 complexes with F···HF hydrogen bonds in a wide range 0.5-48 kcal/mol by means of quantum chemical calculations equilibrium geometries, complexation energies, vibrational frequencies and corresponding force constants were calculated (MP2/aug-cc-pVTZ). It is shown, that properties of a hydrogen bond are more strictly correlated with the values of force constants than with vibrational frequencies. Easy-to-use equations for estimations of hydrogen bond energy ∆E and geometry (r, r) based on k and k values are proposed.
在这项工作中，讨论了质子供体基团伸缩振动常数k和分子间伸缩力常数k在评估氢键强度和几何结构方面的适用性。通过量子化学计算（MP2/aug-cc-pVTZ），对一组30个具有F···HF氢键、氢键能在0.5 - 48 kcal/mol范围内的配合物，计算了其平衡几何结构、络合能、振动频率和相应的力常数。结果表明，氢键的性质与力常数的相关性比与振动频率的相关性更为严格。提出了基于k和k值估算氢键能∆E和几何结构（r，r）的易用方程。
