Solvent Effect on Electronegativity, Hardness, Condensed Fukui Functions, and Softness, in a Large Series of Diatomic and Small Polyatomic Molecules:  Use of the EFP Model

Abstract

The effect of solvent on the electronegativity, hardness, and condensed Fukui function, and atomic softness for a set of diatomic and small polyatomic molecules and ions has been studied using the effective fragment potential (EFP) model. The binding function was used for monitoring the solvation of the molecule. We do not observe a decrease in the HOMO-LUMO gap in the solvent. All anions show a significant change in the chemical potential. Both HOMO and LUMO energy levels decrease in the solvent phase as compared to the gas phase. For the major part of the acids, the increase in the LUMO orbital energy is larger than in the HOMO orbital energy. For the group of salts, we observe an increase in the LUMO energy level and a similar decrease in the HOMO energy level, resulting in a small change in the chemical potential. The importance of the change in the wave function upon solvation was shown through an analysis of the relaxation part in the hardness and condensed Fukui function. Very close values found for the same ions in molecules such as LiH, LiF, NaH, NaF, and LiF indicate that in these cases very good separated ion pairs are present.

Fullerene-based materials for solar cell applications: design of novel acceptors for efficient polymer solar cells – a DFT study

“…Due to the slight dependence of the considered properties on the solvent effect, 65 we expect that the obtained correlations can also be applicable under the presence of solvent. It is worth mentioning that we have performed our calculations in the vacuum in order to find a simple approach for theoretical prediction of V OC of a solar cell.…”

Application of a semi‐empirical dispersion correction for modeling water clusters

“…In addition to HF and DFT, these methods include time‐dependent DFT, singly excited configuration interaction, multiconfiguration self‐consistent field, MP2 and multireference MP2 (MRPT2), and CC theory . Most EFP1 applications have been focused on determining aqueous solvent effects on ground and electronically excited state QM properties and processes . However, EFP1 does not contain the dispersion interaction that can be important.…”

Intrinsic Nucleofugality Scale within the Framework of Density Functional Reactivity Theory

“…The ultimate goal is thereby to create a useful predicting tool for experimental organic chemists. Following our previous research of solvent effects on reactivity descriptors, [17][18][19] we will examine how nucleofugality values are altered in solution. The construction of this nucleofugality scale bears an analogy with the electrophilicity scale for radicals, previously proposed by De Vleeschouwer et al 20 This approach will also enable us to test the rule of thumb in organic chemistry, stating that good leaving groups are the conjugate bases of strong acids.…”