Benzene⋯acetylene: a structural investigation of the prototypical CH⋯π interaction

Literature Information

Publication Date 2014-03-31
DOI 10.1039/C4CP00845F
Impact Factor 3.676
Authors

Nathan W. Ulrich, Nathan A. Seifert, Rachel E. Dorris, Rebecca A. Peebles, Brooks H. Pate, Sean A. Peebles


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Abstract

The structure of a prototype CH⋯π system, benzene⋯acetylene, has been determined in the gas phase using Fourier-transform microwave spectroscopy. The spectrum is consistent with an effective C6v structure with an H⋯π distance of 2.4921(1) Å. The HCCH subunit likely tilts by ∼5° from the benzene symmetry axis. The dipole moment was determined to be 0.438(11) D from Stark effect measurements. The observed intermolecular distance is longer than in similar benzene⋯HX complexes and than the distances observed in the benzene⋯HCCH cocrystal and predicted by many high level ab initio calculations; however, the experimentally estimated binding energy of 7.1(7) kJ mol−1 is similar to previously studied benzene⋯HX complexes. Several additional sets of transitions were observed in the rotational spectrum, likely corresponding to excited states arising from low energy intermolecular vibrational modes of the dimer.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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