Potential energy curves for cation-pi interactions: off-axis configurations are also attractive
Michael S Marshall1, Ryan P Steele, Kanchana S Thanthiriwatte
1Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30332-0400, USA.
Abstract:
Accurate potential energy surfaces for benzene.M complexes (M = Li+, Na+, K+, and NH4+) are obtained using coupled-cluster theory through perturbative triple excitations, CCSD(T). Our computations show that off-axis cation-pi interactions, where the cation is not directly above the aromatic ring, can be favorable and may influence molecular recognition. Even perpendicular, side-on interactions retain 18-32% of their pi-face interaction energy in the gas phase, making their bond strengths comparable to hydrogen bonds in the gas phase. Solvent effects have been explored for each complex using the polarizable continuum model.
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