1 Centre for Research in Molecular Modeling (CERMM) and PROTEO , Department of Chemistry and Biochemistry , Concordia University , 7141 Sherbrooke Street West , Montréal , Québec H4B 1R6 , Canada.

S-aromatic motifs are important noncovalent forces for protein stability and function but remain poorly understood. Hence, we performed quantum calculations at the MP2(full)/6-311++G(d,p) level on complexes between Cys (H(2)S, MeSH) and Met (Me(2)S) models with models of Phe (benzene, toluene), Trp (indole, 3-methylindole), Tyr (phenol, 4-methylphenol), and His (imidazole, 4-methylimidazole). The most stable gas-phase conformers exhibit binding energies of -2 to -6 kcal/mol, and the S atom lies...