NDLI: Roles of electrostatic interaction and dispersion in CH···CH, CH···π, and π···π ethylene dimers

Content Provider	Springer Nature Link
Author	Cao, Ye Wong, Ming Wah
Copyright Year	2014
Abstract	Ab initio molecular orbital calculations were performed up to the CCSD(T)/CBS level to investigate the roles of the electrostatic interaction and dispersion in three basic types of intermolecular interaction, namely CH···CH, CH···π, and π···π interactions, in D2d, C2v, and Ci ethylene dimers, respectively. SAPT energy decomposition revealed that the electrostatic interaction is more significant than expected, with its value being close to that of the net interaction energy. Dispersion is the largest stabilizing force and it plays the main role in balancing out exchange repulsion. This balance is related to the proposed concept of “contact.” The roles of the σ and π electrons were distinguished in the electrostatic interaction by performing distributed multipole analysis and in dispersion by performing frozen-orbital SAPT (fo-SAPT) calculations. The electrostatic part of the interaction energy for each ethylene dimer can be understood as either a quadrupole–quadrupole attraction or the attraction between C and H atoms. (Electron pair)–(electron pair) contributions to the dispersion were calculated by the fo-SAPT method to shed light on the nature of dispersion. In these dimers, contributions to the dispersion can arise from π↔π, σ↔π, or σ↔σ electron-pair interactions. Surprisingly, σ↔π interactions dominate the dispersion in all three ethylene dimers. The π↔π contribution is very small, even in the displaced parallel structure (Ci). The σ↔σ interaction contributes to intermolecular binding by helping the dispersion to balance out exchange repulsion, but this interaction is limited to the most stable D2d structure, which is characterized by four pairs of close dihydrogen contacts. The concept of an electron-pair “contact” was introduced to describe the exchange–dispersion balance. The D2d dimer is stabilized by a large number of such contacts. Figure Interplay of electrostatic interaction and dispersion in CH···CH, CH···π, and π···π ethylene dimers
Starting Page	1
Ending Page	12
Page Count	12
File Format	PDF
ISSN	16102940
Journal	Journal of Molecular Modeling
Volume Number	20
Issue Number	4
e-ISSN	09485023
Language	English
Publisher	Springer Berlin Heidelberg
Publisher Date	2014-03-28
Publisher Place	Berlin, Heidelberg
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Ethylene dimer Intermolecular interaction Energy decomposition π···π interaction CH···π interaction Computer Applications in Chemistry Molecular Medicine Computer Application in Life Sciences Characterization and Evaluation of Materials Theoretical and Computational Chemistry
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Physical and Theoretical Chemistry Computational Theory and Mathematics Catalysis Inorganic Chemistry Computer Science Applications

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