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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Coordination of methanol clusters to benzene: A computational study
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Coordination of methanol clusters to benzene: A computational study

机译：甲醇团簇与苯的配位：计算研究

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Benzene-methanol cluster structures were investigated with theoretical chemistry methods to describe the microsolvation of benzene and the benzene-methanol azeotrope. Benzene-methanol (MeOH) clusters containing up to six methanol molecules have been calculated by ab initio [MP2/6-311++G(d,p)// MP2/6-31+G(d,p) + BSSE correction] method. The BSSE was found quite large with this basis set, hence, different extrapolation schemes in combination with the aug-cc-pVxZ basis sets have been used to estimate the complete basis set limit of the MP2 interaction energy [ΔE(MP2/CBS)]. For smaller clusters, n ≥ 3, DFT procedures (DFTB+, MPWB1K, M06-2X) have also been applied. Geometries obtained for these clusters by M06-2X and MP2 calculations are quite similar. Based on the MP2/CBS results, the most stable C_6H_6(MeOH) _3 cluster is characterized by a hydrogen bonded MeOH trimer chain interacting with benzene via π???H-O and O???H- C(benzene) hydrogen bonds. Larger benzene-MeOH clusters with n ≥ 4 consist of cyclic (MeOH)_n subclusters interacting with benzene by dispersive forces, to be denoted by C_6H_6 + (MeOH)_n. Interaction energies and cooperativity effects are discussed in comparison with methanol clusters. Besides MP2/CBS calculations, for selected larger clusters the M06-2X/6-311++G(d,p)//M06-2X/6-31+G(d,p) procedure including the BSSE correction was also used. Interaction energies obtained thereby are usually close to the MP2/CBS limit. To model the benzene-MeOH azeotrope, several structures for (C_6H_6)_2(MeOH)_3 clusters have been calculated. The most stable structures contain a tilted T-shaped benzene dimer interacting by π???H-O and O???H-C (benzene) hydrogen bonds with a (MeOH)_3 chain. A slightly less negative interaction energy results for a parallel displaced benzene sandwich dimer with a (MeOH)_3 chain atop of one of the benzene molecules.
机译：用理论化学方法研究了苯甲醇混合物的结构，以描述苯和苯甲醇共沸物的微溶剂化。通过从头算[MP2 / 6-311 ++ G（d，p）// MP2 / 6-31 + G（d，p）+ BSSE校正计算出最多包含六个甲醇分子的苯甲醇（MeOH）簇] 方法。发现该基本集的BSSE很大，因此，已将不同的外推方案与aug-cc-pVxZ基本集结合使用，以估计MP2相互作用能的完整基本集极限[ΔE（MP2 / CBS）] 。对于较小的群集，n≥3，还应用了DFT程序（DFTB +，MP​​WB1K，M06-2X）。通过M06-2X和MP2计算获得的这些簇的几何形状非常相似。基于MP2 / CBS结果，最稳定的C_6H_6（MeOH）_3簇的特征在于氢键结合的MeOH三聚体链通过π-H-O和O-H-C（苯）氢键与苯相互作用。 n≥4的较大苯-MeOH团簇由通过分散力与苯相互作用的环状（MeOH）_n子簇组成，表示为C_6H_6 +（MeOH）_n。与甲醇团簇相比，讨论了相互作用能和协同作用。除了MP2 / CBS计算，对于选定的较大群集，还使用了包括BSSE校正在内的M06-2X / 6-311 ++ G（d，p）// M06-2X / 6-31 + G（d，p）程序。由此获得的相互作用能通常接近MP2 / CBS极限。为了模拟苯-MeOH共沸物，已经计算了（C_6H_6）_2（MeOH）_3团簇的几种结构。最稳定的结构含有一个倾斜的T形苯二聚体，它通过与（MeOH）_3链的π-H和O-H-C（苯）氢键相互作用。对于在苯分子之一的顶部具有（MeOH）3链的平行置换的苯夹心二聚体，产生较小的负相互作用能。

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