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Electron Density Characteristics in Bond Critical Point (QTAIM) versus Interaction Energy Components (SAPT): The Case of Charge-Assisted Hydrogen Bonding

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journal contribution
posted on 12.01.2012, 00:00 by Barbara Bankiewicz, Piotr Matczak, Marcin Palusiak
Charge-assisted hydrogen bonds (CAHBs) of N–H···Cl, N–H···Br, and P–H···Cl type were investigated using advanced computational approach (MP2/aug-cc-pVTZ level of theory). The properties of electron density function defined in the framework of Quantum Theory of Atoms in Molecules (QTAIM) were estimated as a function of distance in H-bridges. Additionally, the interaction energy decomposition was performed for H-bonded complexes with different H-bond lengths using the Symmetry-Adapted Perturbation Theory (SAPT). In this way both QTAIM parameters and SAPT energy components could be expressed as a function of the same variable, that is, the distance in H-bridge. A detailed analysis of the changes in QTAIM and SAPT parameters due to the changes in H···A distance revealed that, over some ranges of H···A distances, electrostatic, inductive and dispersive components of the SAPT interaction energy show a linear correlation with the value of the electron density at H-BCP ρBCP. The linear relation between the induction component, Eind, and ρBCP confirms numerically the intuitive expectation that the ρBCP reflects directly the effects connected with the sharing of electron density between interacting centers. These conclusions are important in view of charge density studies performed for crystals in which the distance between atoms results not only from effects connected with the interaction between atomic centers directly involved in bonding, but also from packing effects which may strongly influence the length of the H-bond.