Characterization of cooperative effects in linear alpha-glycylglycine clusters

The aspects of N-H...O=CNH, N-H...O=CO and C-H...O=CNH interactions are analyzed by applying ab initio and DFT methods as well as Bader theory. We investigated geometry, binding energies, (17)O, (15)N chemical shift tensors, and Atoms in Molecules (AIM) properties of alpha-glycylglycine (alpha-glygly) clusters, via MP2, B3LYP and PW91(XC) methods. Dimer stabilization energies and equilibrium geometries are studied in various levels of theory. MP2 and DFT calculations reveal that for alpha-glygly clusters, stability of N-H...O and C-H...O hydrogen bonds are enhanced significantly as a result of cooperativity effects. Furthermore, a covalent nature is also detected for some hydrogen bondings. The n-dependent trend of (17)O and (15)N chemical shift tensors was reasonably correlated with cooperative effects in hydrogen-bond interactions. Regarding the various N-H...O=CNH, N-H...O=CO and C-H...O=CNH hydrogen bondings, capability of the alpha-glygly clusters for electron localization at the N-H...O and C-H...O bond critical points, depends on the cluster size. This leads to cooperative changes in the hydrogen-bond length and strength as well as (17)O and (15)N chemical shift tensors.