Face-to-Face Arene-Arene Binding Energies: Dominated by Dispersion but Predicted by Electrostatic and Dispersion/Polarizability Substituent Constants.
Summary of "Face-to-Face Arene-Arene Binding Energies: Dominated by Dispersion but Predicted by Electrostatic and Dispersion/Polarizability Substituent Constants."
Parallel 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 ∑|σ(m)| values of the substituted aromatics. It is proposed that a substituent |σ(m)| value informs on both the aromatic substituent dispersion/polarizability and the effect the substituent has on the aromatic electrostatics. Supporting this hypothesis, a combination of electrostatic (∑σ(m)) and dispersion/polarizability (∑M(r)) substituent constant terms gives an excellent, and statistically significant, correlation with the benzene-substituted benzene binding energy. Symmetry adapted perturbation theory energy decomposition calculations show the dominant attractive force is dispersion; however, the sum of all nonelectrostatic forces is essentially a constant, while the electrostatic component varies significantly. This explains the importance of including an electrostatic term when predicting benzene-substituted benzene binding energies.
Affiliation
Department of Chemistry, Saint Louis University , 3501 Laclede Avenue, Saint Louis, Missouri 63103, United States.
Journal Details
This article was published in the following journal.
Name: Journal of the American Chemical Society
ISSN: 1520-5126
Pages: 3854-62
Links
- PubMed Source: http://www.ncbi.nlm.nih.gov/pubmed/21361361
- DOI: http://dx.doi.org/10.1021/ja105975a
Medical and Biotech [MESH] Definitions
Epoxide Hydrolases
Enzymes that catalyze reversibly the formation of an epoxide or arene oxide from a glycol or aromatic diol, respectively.
Education, Distance
Education via communication media (correspondence, radio, television, computer networks) with little or no in-person face-to-face contact between students and teachers. (ERIC Thesaurus, 1997)
Vertical Dimension
The length of the face determined by the distance of separation of jaws. Occlusal vertical dimension (OVD or VDO) or contact vertical dimension is the lower face height with the teeth in centric occlusion. Rest vertical dimension (VDR) is the lower face height measured from a chin point to a point just below the nose, with the mandible in rest position. (From Jablonski, Dictionary of Dentistry, 1992, p250)
Esthetics, Dental
Skills, techniques, standards, and principles used to improve the art and symmetry of the teeth and face to improve the appearance as well as the function of the teeth, mouth, and face. (From Boucher's Clinical Dental Terminology, 4th ed, p108)
Maxillary Artery
A branch of the external carotid artery which distributes to the deep structures of the face (internal maxillary) and to the side of the face and nose (external maxillary).
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