Cart
Letter
Beyond the Benzene Dimer: An Investigation of the Additivity of π−π Interactions
Full Text HTML
Hi-Res PDFPurchase the full-text
- PDF/HTML,
figures/images,
references and tables,
(where available)
Section:Abstract
The benzene dimer is the simplest prototype of π−π interactions and has been used to understand the fundamental physics of these interactions as they are observed in more complex systems. In biological systems, however, aromatic rings are rarely found in isolated pairs; thus, it is important to understand whether aromatic pairs remain a good model of π−π interactions in clusters. In this study, ab initio methods are used to compute the binding energies of several benzene trimers and tetramers, most of them in 1D stacked configurations. The two-body terms change only slightly relative to the dimer, and except for the cyclic trimer, the three- and four-body terms are negligible. This indicates that aromatic clusters do not feature any large nonadditive effects in their binding energies, and polarization effects in benzene clusters do not greatly change the binding that would be anticipated from unperturbed benzene−benzene interactions, at least for the 1D stacked systems considered. Three-body effects are larger for the cyclic trimer, but for all systems considered, the computed binding energies are within 10% of what would be estimated from benzene dimer energies at the same geometries.
Citing Articles
Citation data is made available by participants in CrossRef's Cited-by Linking service. For a more comprehensive list of citations to this article, users are encouraged to perform a search in SciFinder.
This article has been cited by 27 ACS Journal articles (5 most recent appear below).
Long, Directional Interactions in Cofacial Silicon Phthalocyanine Oligomers
Yang Yang, Brian Samas, Vance O. Kennedy, Dainius Macikenas, Brian L. Chaloux, Jacob A. Miller, Richard L. Speer, Jr., John Protasiewicz, A. Alan Pinkerton, and Malcolm E. KenneyThe Journal of Physical Chemistry A2011 115 (45), 12474-12485Long, Directional Interactions in Cofacial Silicon Phthalocyanine Oligomers
Yang Yang, Brian Samas, Vance O. Kennedy, Dainius Macikenas, Brian L. Chaloux, Jacob A. Miller, Richard L. Speer, Jr., John Protasiewicz, A. Alan Pinkerton, and Malcolm E. KenneyThe Journal of Physical Chemistry A2011 115 (45), 12474-12485Single crystal structures have been determined for the three cofacial, oxygen-bridged, silicon phthalocyanine oligomers, [((CH3)3SiO)2(CH3)SiO](SiPcO)2–4[Si(CH3)(OSi(CH3)3)2], and for the corresponding monomer. The data for the oligomers give structural ...
A Promising Approach to Obtain Excellent n-Type Organic Field-Effect Transistors: Introducing Pyrazine Ring
Xian-Kai Chen, Jing-Fu Guo, Lu-Yi Zou, Ai-Min Ren, and Jian-Xun FanThe Journal of Physical Chemistry C2011 115 (43), 21416-21428A Promising Approach to Obtain Excellent n-Type Organic Field-Effect Transistors: Introducing Pyrazine Ring
Xian-Kai Chen, Jing-Fu Guo, Lu-Yi Zou, Ai-Min Ren, and Jian-Xun FanThe Journal of Physical Chemistry C2011 115 (43), 21416-21428The effects of the pyrazine ring on the geometrical and electronic structures, molecular stacking motifs, carrier injection, and transport properties as well as electronic band structures for some typical molecules with pyrazines (such as tetracene, ...
Aromatic–Aromatic Interactions in Proteins: Beyond the Dimer
Esteban Lanzarotti, Rolf R. Biekofsky, Darío A. Estrin, Marcelo A. Marti, and Adrián G. TurjanskiJournal of Chemical Information and Modeling2011 51 (7), 1623-1633Aromatic–Aromatic Interactions in Proteins: Beyond the Dimer
Esteban Lanzarotti, Rolf R. Biekofsky, Darío A. Estrin, Marcelo A. Marti, and Adrián G. TurjanskiJournal of Chemical Information and Modeling2011 51 (7), 1623-1633Aromatic residues are key widespread elements of protein structures and have been shown to be important for structure stability, folding, protein–protein recognition, and ligand binding. The interactions of pairs of aromatic residues (aromatic dimers) ...
A Comparative Study for Molecular Dynamics Simulations of Liquid Benzene
Cen-Feng Fu and Shan Xi TianJournal of Chemical Theory and Computation2011 7 (7), 2240-2252A Comparative Study for Molecular Dynamics Simulations of Liquid Benzene
Cen-Feng Fu and Shan Xi TianJournal of Chemical Theory and Computation2011 7 (7), 2240-2252The classical equilibrium and nonequilibrium molecular dynamics simulations for liquid benzene, the prototypical aromatic π–π interaction system, are performed using a variety of molecular force fields, OPT-FF, AMBER 03, general AMBER force field (GAFF), ...
Face-to-Face Arene−Arene Binding Energies: Dominated by Dispersion but Predicted by Electrostatic and Dispersion/Polarizability Substituent Constants
Michelle Watt, Laura K. E. Hardebeck, Charles C. Kirkpatrick, and Michael LewisJournal of the American Chemical Society2011 133 (11), 3854-3862Face-to-Face Arene−Arene Binding Energies: Dominated by Dispersion but Predicted by Electrostatic and Dispersion/Polarizability Substituent Constants
Michelle Watt, Laura K. E. Hardebeck, Charles C. Kirkpatrick, and Michael LewisJournal of the American Chemical Society2011 133 (11), 3854-3862Parallel face-to-face arene−arene complexes between benzene and substituted benzenes have been investigated at the MP2(full)/6-311G** and M05-2X/6-311G** levels of theory. A reasonably good correlation was found between the binding energies and the ∑|σm| ...
Tools
-
Add to Favorites
-
Download Citation
-
Email a Colleague -
Permalink
Order Reprints
Rights & Permissions
Citation Alerts
History
- Published In Issue November 24, 2005
- Received September 20, 2005
ACS
Network
Facebook
Tweet This
CiteULike
Newsvine
Digg This
Delicious
