Nolasco Mariela M, Coimbra Mariana Matos, Parker Stewart F, Vaz Pedro D, Ribeiro-Claro Paulo J A
CICECO-Instituto de Materiais de Aveiro, Departamento de Química, Universidade de Aveiro, 3810-193 Aveiro, Portugal.
ISIS Neutron & Muon Source, STFC Rutherford Appleton Laboratory, Chilton, Didcot, Oxfordshire OX11 0QX, UK.
Molecules. 2022 Nov 7;27(21):7661. doi: 10.3390/molecules27217661.
In this work, the structural dynamics of the chloromethanes CCl, CHCl and CHCl were evaluated through a computational spectroscopy approach by comparing experimental inelastic neutron scattering (INS) spectra with the corresponding simulated spectra obtained from periodic DFT calculations. The overall excellent agreement between experimental and calculated spectra allows a confident assignment of the vibrational features, including not only the molecular fundamental modes but also lattice and combination modes. In particular, an impressive overtone sequence for CHCl is fully described by the simulated INS spectrum. In the CCl spectrum, the splitting of the ν3 mode at ca. 765-790 cm is discussed on the basis of the Fermi resonance vs. crystal splitting controversy.
在这项工作中，通过将实验非弹性中子散射（INS）光谱与从周期性密度泛函理论（DFT）计算获得的相应模拟光谱进行比较，采用计算光谱学方法评估了氯甲烷CCl、CHCl和CHCl的结构动力学。实验光谱与计算光谱之间总体上的出色吻合使得能够可靠地归属振动特征，不仅包括分子基模，还包括晶格模和组合模。特别是，模拟的INS光谱完整地描述了CHCl令人印象深刻的泛音序列。在CCl光谱中，基于费米共振与晶体分裂之争，讨论了约765 - 790 cm处ν3模式的分裂。
