Experimental and theoretical determination of the accurate interaction energies in benzene–halomethane: the unique nature of the activated CH/π interaction of haloalkanes

Asuka Fujii; Kenta Shibasaki; Takaki Kazama; Ryousuke Itaya; Naohiko Mikami; Seiji Tsuzuki

doi:10.1039/B717053J

Experimental and theoretical determination of the accurate interaction energies in benzene–halomethane: the unique nature of the activated CH/π interaction of haloalkanes†

Asuka Fujii,*^a Kenta Shibasaki,^a Takaki Kazama,^a Ryousuke Itaya,^a Naohiko Mikami^a and Seiji Tsuzuki*^b

* Corresponding authors

^a Department of Chemistry, Graduate School of Science, Tohoku University, Sendai, Japan
E-mail: asukafujii@mail.tains.tohoku.ac.jp

^b National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba, Ibaraki, Japan
E-mail: s.tsuzuki@aist.go.jp

Abstract

The CH/π interaction energies between benzene and halomethanes (CH₂Cl₂ and CHCl₃) were accurately determined. Two-color ionization spectroscopy was applied to the benzene–CH₂Cl₂ and –CHCl₃clusters, and the binding energies in the neutral ground state, i.e. the CH/π interaction energies in these model cluster systems, were precisely evaluated on the basis of the dissociation threshold measurements of the clusters in the cationic state and the ionization potential value of the bare molecule. The experimentally determined interaction energies were 3.8 ± 0.2 and 5.2 ± 0.2 kcal mol⁻¹ for benzene–CH₂Cl₂ and –CHCl₃ respectively, and the remarkable enhancement of the CH/π interaction energy with chlorine-substitution was quantitatively confirmed. The experimental interaction energies were well reproduced by the high-level ab initio calculations. The theoretical calculations clarified the unique nature of the activation of the CH/π interaction by the chlorine-substitution.

This article is part of the themed collection: Stacking interactions

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DOI: https://doi.org/10.1039/B717053J
Article type: Paper
Submitted: 05 Nov 2007
Accepted: 07 Jan 2008
First published: 08 Feb 2008

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Phys. Chem. Chem. Phys., 2008,10, 2836-2843

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Experimental and theoretical determination of the accurate interaction energies in benzene–halomethane: the unique nature of the activated CH/π interaction of haloalkanes

A. Fujii, K. Shibasaki, T. Kazama, R. Itaya, N. Mikami and S. Tsuzuki, Phys. Chem. Chem. Phys., 2008, 10, 2836 DOI: 10.1039/B717053J

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Physical Chemistry Chemical Physics

Experimental and theoretical determination of the accurate interaction energies in benzene–halomethane: the unique nature of the activated CH/π interaction of haloalkanes†

Abstract

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Experimental and theoretical determination of the accurate interaction energies in benzene–halomethane: the unique nature of the activated CH/π interaction of haloalkanes

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