Structural Chemistry

, Volume 20, Issue 1, pp 11–20

Geometries and stabilities of various configurations of benzene dimer: details of novel V-shaped structure revealed

Original Research
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Abstract

Benzene dimer configurations namely T-shaped, parallel-displaced, sandwich, and V-shaped that were proposed by experimental studies are investigated using second- and fourth-order Møller–Plesset perturbation theory. The MP2 method with aug-cc-pVDZ and aug-cc-pVTZ basis sets unequivocally shows that the parallel-displaced configuration is considerably more stable than T-shaped structure. On the other hand, the MP4(SDTQ)/aug-cc-pVDZ level predicts that the T-shaped and parallel-displaced configurations are nearly isoenergetic, which is parallel to the previous results of estimated CCSD(T)/CBS level reported recently. The lowest energy T-shaped configuration is stabilized by 0.17 kcal/mol over the parallel-displaced configuration at the MP4(SDTQ)/aug-cc-pVDZ level. Although the structures of all the four different types of configurations are found to be stable at both MP2 and full MP4 methods, the V-shaped configuration is the least stable among them. The calculated interaction energy of −2.3 kcal/mol for the lowest energy T-shaped structure at the MP4(SDTQ)/aug-cc-pVDZ level is in good agreement with the experimental value of −2.4 ± 0.4 kcal/mol. We conclude that the MP4(SDTQ) with a reasonably good basis set can be used for systems involving π–π interactions to obtain qualitative and quantitative results.

Keywords

Benzene dimer π–π interactions Møller–Plesset perturbation theory Electron correlation Interaction energies 

Copyright information

© Springer Science+Business Media, LLC 2009

Authors and Affiliations

  1. 1.Department of Chemistry, Interdisciplinary Nanotoxicity CenterJackson State UniversityJacksonUSA

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