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The quantum mechanical density functional theory methods were used to study the complexes of glycoxal diimine ligands and 2+ cations of the first row transition metal elements. The results offered insight into the total energies, binding energies, and molecular structures of model octahedral coordination of complexes.

The surface-bulk partition of nonionic surfactants was predicted by calculating chemical potential differences using two simulation boxes representing the surface and the bulk phases separately. A published coarse grained force field was modified and validated for this application. Thermodynamic integration (TI) was applied to compute excess chemical potentials. The high concentration surface was stabilized by applying an external harmonic potential, and the bulk was treated as ideal solution, which was confirmed by simulation using a lattice model at conditions near the critical micelle concentration (∼10-5 mol/L). Based on the calculated chemical potential differences with precision of ca. 1 kJ/mol, the equilibria of surface-bulk concentration was predicted well in comparison with the experimental data. [ABSTRACT FROM AUTHOR]

To achieve a systematic understanding of the influence of microsolvation on the electron accepting behaviors of nucleobases, the reliable theoretical method (B3LYP/DZP++) has been applied to a comprehensive conformational investigation on the uracil−water complexes U−(H2O)n (n = 1, 2, 3) in both neutral and anionic forms. For the neutral complexes, the conformers of hydration on the O2 of uracil are energetically favored. However, hydration on the O4 atom of uracil is more stable for the radical anions. The electron structure analysis for the H-bonding patterns reveal that the CH···OH2 type H-bond exists only for di- and trihydrated uracil complexes in which a water dimer or trimer is involved. The electron density structure analysis and the atoms-in-molecules (AIM) analysis for U−(H2O)n suggest a threshold value of the bond critical point (BCP) density to justify the CH···OH2 type H-bond; that is, CH···OH2 could be considered to be a H-bond only when its BCP density value is equal to or larger than 0.010 au. The positive adiabatic electron affinity (AEA) and vertical detachment energy (VDE) values for the uracil−water complexes suggest that these hydrated uracil anions are stable. Moreover, the average AEA and VDE of U−(H2O)n increase as the number of the hydration waters increases. [ABSTRACT FROM AUTHOR]