Title

Interactions Involving Aromatic Systems: Benzene + Acetylene

Document Type

Article

Journal/Book Title

International Journal of Quantum Chemistry

Publication Date

1984

Publisher

Wiley

Volume

26

Issue

11

First Page

201

Last Page

208

DOI

10.1002/qua.560260721

Abstract

Various configurations of the system composed of benzene and acetylene are investigated in an effort to identify the most stable. The total interaction energy is computed as the sum of the dispersion energy ED and ΔESCF, the interaction energy calculated by ab initio molecular orbital methods. Pairwise summation schemes of both the atom–atom and bond–bond types are used to evaluate ED. The most stable structure is found to be that in which the acetylene approaches benzene from above and is oriented such that it lies directly along the C6 axis of benzene. Although the contribution of dispersion to the total interaction energy is dominant, the smaller electrostatic component plays a crucial role in controlling the relative orientations of the two molecules. Indeed, it is possible to select the most stable configuration solely on grounds of the most favorable quadrupole–quadrupole interaction. The likelihood of observation of this configuration is further confirmed by consideration of basis set extension and entropic effects.

Comments

Originally published by Wiley-Blackwell in the International Journal of Quantum Chemistry.

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