Solvent Effect on the Global and Atomic DFT-Based Reactivity Descriptors Using the Effective Fragment Potential Model. Solvation of Ammonia

Abstract

The effective fragment potential (EFP) model has been used to study the effect of adding increasing numbers of the water molecules on several DFT-based reactivity descriptors of NH 3 . The HOMO-LUMO gap and electrophilic hardness are seen to increase with addition of water molecules. The importance on the wave function relaxation in the solvent effect on ammonia's properties is shown when analyzing the relaxation part in the electrophilic hardness and condensed Fukui function for the nitrogen atom. An increase in the atomic softness for the nitrogen atom with decreasing the global softness is observed. The saturation point for solvatation of ammonia was located around a cluster with 16 molecules of water. Atomic properties such as the Mulliken population, condensed Fukui function, and atomic softness for nitrogen and electrophilic global properties such as the hardness and its components for dilute solutions are predicted faithfully.

Model compound release from DL‐lactide/ε‐caprolactone copolymers and evaluation of specific interactions by molecular modeling

“…Thus, the condensed Fukui function is showing the effect of aza‐N on the porphyrin macrocycle. Note that negative values for a condensed Fukui function may also be obtained in a reactivity study 52 and constitute in our case an indicator that a hard system is present.…”

The Interaction of Water with cis and trans {Ru(bpy)2(PTA)2}2+ (PTA = 1,3,5‐Triaza‐7‐phosphaadamantane) Studied by Neutron Scattering and Ab Initio Calculations

“…These can potentially interact with the low lying unoccupied water orbitals, forming hydrogen bonds. However, the quite small negative calculated Mulliken charge of –0.15 at nitrogen (compared to –0.75 at nitrogen in gas phase ammonia) does not indicate a strong driving force for the formation of hydrogen bonds. Electronic excitation, that shifts electron density into the unoccupied bipyridyl located orbitals is thus likely to affect the water orientation and coordination around these complexes.…”

Can Electrophilicity Act as a Measure of the Redox Potential of First‐Row Transition Metal Ions?

“…The chemical potential, however, increases upon going from the gas phase to solution. [39] Less significant changes in the chemical potential are observed for the most elaborate representations of the discrete solvent shells. This finding can be explained by considering the charge dependency of the change in the chemical potential, as discussed by PØrez et al [21] Since the inclusion of more water shells results in a delocalisation of the charge away from the metal core, the chemical potential decreases less.…”