Frequency shifts and interaction strength of model hydrogen-bonded systems: new NBO and QTAIM characteristics

An innovative theoretical study of intermolecular properties of standard hydrogen-bonded complexes of H2O center dot center dot center dot HCF3, NH3 center dot center dot center dot HCF3, H2O center dot center dot center dot HF, and NH3 center dot center dot center dot HF is presented in this work. Several computational strategies were used, so initially the MP2/6-311++G(d,p) level of theory was applied to determine the optimized geometries by which the structural parameters, electronic properties, and the stretch vibration modes of these systems were examined. By taking into account the infrared spectrum analysis, the frequency shifted either to the red- or blue-region is the principal interpretation upon formation of intermolecular complexes. Due to this, the analysis of the interaction strengths corroborates with these vibration behaviors, and besides, the Natural Bond Orbital calculations revealed systematic changes in the percentage of the s and p orbitals, by which the stretch deformations on the proton donors (HF and HCF3) could be understood. In advance, it was quoted the appearing of intermolecular covalence in these complexes, and this event could be theoretically discovered through the topological computations based on the Bader's Quantum Theory of Atoms in Molecules.