de Oliveira Rhuiago M, Roncaratti Luiz F, de Macedo Luiz Guilherme M, Gargano Ricardo
Instituto de Física, Universidade de Brasília (UnB), PO Box 04455, Brasília, DF, 70919-970, Brazil.
Faculdade de Biotecnologia, Instituto de Ciências Biológicas, Universidade Federal do Pará (UFPA), Belém, PA, 66075-110, Brazil.
J Mol Model. 2017 Mar;23(3):87. doi: 10.1007/s00894-017-3269-0. Epub 2017 Feb 21.
This investigation generated rovibrational energies and spectroscopic constants for systems of CCl with Ng (Ng = He, Ne, Ar), O, DO and ND from scattering experimental data, and the results presented are of interest for microwave spectroscopy studies of small halogenated molecules. The rovibrational spectra were obtained through two different approaches (Dunham and DVR) within the improved Lennard Jones (ILJ) model. Spectra were also generated within ordinary Lennard Jones and deviations suggest that the ILJ model should be preferred due to interactions beyond dispersion forces presented in these systems. Data from the literature and additional high level quantum mechanical calculations presented in this work show that these systems should not be considered as van der Waals complexes due to halogen bonding (HB) interactions, and this is especially true for the CCl-DO and CCl-ND complexes. The charge displacement from the latter systems are one order of magnitude higher than the values from literature for CCl and He, Ne, Ar and O systems, and show significant deviations between DFT and Hartree-Fock values not previously reported in the literature.
本研究从散射实验数据中生成了CCl与Ng（Ng = He、Ne、Ar）、O、DO和ND体系的振转能量及光谱常数，所得结果对于小卤代分子的微波光谱研究具有重要意义。振转光谱是在改进的 Lennard Jones（ILJ）模型内通过两种不同方法（Dunham和DVR）获得的。普通Lennard Jones模型也生成了光谱，偏差表明由于这些体系中存在色散力之外的相互作用，ILJ模型更具优势。文献数据以及本工作中给出的额外高水平量子力学计算表明，由于卤键（HB）相互作用，这些体系不应被视为范德华复合物，对于CCl-DO和CCl-ND复合物尤其如此。后一种体系的电荷位移比文献中CCl与He、Ne、Ar和O体系的值高一个数量级，并且显示出密度泛函理论（DFT）值与Hartree-Fock值之间存在显著偏差，这在文献中此前未曾报道。
