Interdisciplinary Center for Molecular Materials and Computer-Chemistry-Center, Friedrich-Alexander-University Erlangen-Nürnberg, Nägelsbachstr. 25, 91052 Erlangen, Germany.
Phys Chem Chem Phys. 2011 Aug 21;13(31):14101-9. doi: 10.1039/c1cp20678h. Epub 2011 Jun 24.
For isolated fluoroform (F(3)CH) molecules adsorbed on a hexagonal ice (0001) surface the properties of blue- and red-shifting hydrogen bonds were studied using static density functional theory (DFT) calculations and Car-Parrinello molecular dynamics (CP-MD) simulations. A systematic search by starting from many initial configurations was performed to determine the lowest-energy structures of F(3)CH on the ice surface, and for the optimized geometries the vibrational frequencies were calculated. The local minima structures are analyzed in terms of their coordination to the surface, with special focus on identifying blue-shifting hydrogen bonds via their spectroscopic signature of an increased frequency of the C-H fundamental stretching vibration. Subsequently, by CP-MD simulations the stability of the lowest-energy configurations at finite temperatures was verified and possible transformation pathways connecting the local minima structures were explored.
使用静态密度泛函理论（DFT）计算和 Car-Parrinello 分子动力学（CP-MD）模拟，研究了吸附在六方冰（0001）表面的孤立氟仿（F（3）CH）分子中蓝移和红移氢键的性质。通过从许多初始构型开始的系统搜索，确定了 F（3）CH 在冰表面的最低能量结构，并且针对优化的几何形状计算了振动频率。根据其与表面的配位情况分析局部极小值结构，特别关注通过增加 C-H 基本伸缩振动的频率来识别蓝移氢键。随后，通过 CP-MD 模拟验证了有限温度下最低能量构型的稳定性，并探索了连接局部极小值结构的可能转化途径。
