期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 115, 期 38, 页码 10556-10564出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp206248w
关键词
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资金
- Wissenschaftlich-Technische Zusammenarbeit Osterreich-Ungarn [HU 4/2009]
- Developing Competitiveness of Universities in the South Transdanubian Region [SROP-4.2.1.B-10/2/KONV-2010-0002]
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 [Delta E(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 C6H6(MeOH)(3) cluster is characterized by a hydrogen bonded MeOH trimer chain interacting with benzene via pi center dot center dot center dot H-O and O center dot center dot center dot 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 C6H6 + (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 (C6H6)(2)(MeOH)(3) clusters have been calculated. The most stable structures contain a tilted T-shaped benzene dimer interacting by pi center dot center dot center dot H-O and O center dot center dot center dot 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.
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