Visualizing dispersion interactions through the use of local orbital spaces. Issue 1 (20th October 2016)

• Record Type: Journal Article
• Authors: Wuttke, Axel; Mata, Ricardo A.
• Is Part Of: Journal of computational chemistry. Volume 38:Issue 1(2017)
• Page Start: 15
• Page End: 23
• Publication Date: 2016-10-20
• Subjects: dispersion -- MP2 -- electronic correlation -- molecular interactions -- molecular clusters; Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.24508
• Languages: English
• ISSNs: 0192-8651

Abstract

Abstract : The interpretation of chemical properties/phenomena can often be aided through the use of imagery. The mapping of molecular electrostatic potentials is a prime example, serving as a guideline in the design of novel compounds or understanding transition state stabilization effects. It is today a common tool for theoreticians and experimentalists alike. With the emergence of concepts such as dispersion energy donors, and the overall importance of dispersion in chemical systems, representations targeting such a class of interactions are warranted. In this work, we make use of local orbital analysis to extract dispersion interactions and represent them in a scalar quantity, the Dispersion Interaction Density (DID). A particular advantage of the method is the possibility to represent at the same footing intermolecular and intramolecular interactions in a straightforward fashion from wave function calculations. We present examples for the benzene dimer, several substituted benzenes and a coupled diamondoid molecule. © 2016 Wiley Periodicals, Inc. Abstract : A straightforward scheme is presented for the representation of intermolecular and intramolecular interactions. Comparison to other popular partitioning schemes shows that local correlated methods can be easily applied to rationalize such effects.