Work

Exploring the (Very Flat) Potential Energy Landscape of R−Br⋅⋅⋅π Interactions with Accurate CCSD(T) and SAPT Techniques

Year: 2016

Type: article

Abstract: Halogen bonds involving an aromatic moiety as an acceptor, otherwise known as R−X⋅⋅⋅π interactions, have increasingly been recognized as being important in materials and in protein–ligand complexes. These types of interactions have been the subject of many recent investigations, but little is known about the ways in which the strengths of R−X⋅⋅⋅π interactions vary as a function of the relative geometries of the interacting pairs. Here we use the accurate CCSD(T) and SAPT2+3δMP2 methods to investigate the potential energy landscapes for systems of HBr, HCCBr, and NCBr complexed with benzene. It is found that only the separation between the complexed molecules have a strong effect on interaction strength while other geometric parameters, such as tilting and shifting R−Br⋅⋅⋅π donor relative to the benzene plane, affect these interactions only mildly. Importantly, it is found that the C6v (T‐shaped) configuration is not the global minimum for any of the dimers investigated.

Source: Chemistry - A European Journal

DOI: 10.1002/chem.201603674

Authors: Kevin E. Riley, Mariela Vazquez, Cole Umemura, Christopher Miller, Khanh‐An Tran

Institutions: Xavier University of Louisiana, Texas A&M University

Language: English

Topic: Crystallography and molecular interactions

Subfield: Physical and Theoretical Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Science Foundation, Narodowe Centrum Badań i Rozwoju, National Institute of General Medical Sciences, National Institute on Minority Health and Health Disparities

Awards: BUILD at Xavier, Project Pathways II, Generation of Liver X Receptor Agonists with LXRb Subtype Selectivity using Modern Computational and Chemical Synthetic Methods, Xavier RCMI Center for Cancer Research , RISE Option II at Xavier University of Louisiana