title: Proton-bound homodimers: how are the binding energies related to proton affinities?
abstract: High-level quantum chemical calculations [G3(MP2)-RAD//MP2/6-31+G(d,p)] have been employed to investigate the relationship between the binding energy (BE) of a substrate (X) and its protonated form [H-X]+ with the proton affinity (PA) of the substrate (X) in several series of protonated homodimers ([X...H-X]+). We find that for each series of closely related substrates, the binding energy (BE) is correlated with the proton affinity (PA) in an approximately quadratic manner. Thus, for a given series, the BE initially increases in magnitude with increasing PA, reaches a point of maximum binding, and then becomes smaller as the PA increases further. This behavior can be attributed to the competing effects of the exothermic partial protonation of the substrate and the endothermic partial deprotonation of the protonated substrate. As the PA increases, protonation of X contributes to increased binding but the penalty for partial deprotonation of [H-X]+ also increases. Once the PA becomes sufficiently high, the penalty for the partial deprotonation of [H-X]+ dominates, leading to maximum binding occurring at intermediate PA.
authors: School of Chemistry and Centre of Excellence in Free Radical Chemistry and Biotechnology, University of Sydney, Sydney, NSW 2006, Australia. chan_b@chem.usyd.edu.au
authors: Bun
authors: B
authors: Chan
authors: Janet E
authors: JE
authors: Del Bene
authors: Leo
authors: L
authors: Radom
mesh_terms: D019281:Dimerization; D006860:Hydrogen Bonding; D008956:Models, Chemical; D008958:Models, Molecular; D011522:Protons; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D011522:Protons