Recent Developments of Computational Methods for pKa Prediction Based on Electronic Structure Theory with Solvation Models

The protonation/deprotonation reaction is one of the most fundamental processes in solutions and biological systems. Compounds with dissociative functional groups change their charge states by protonation/deprotonation. This change not only significantly alters the physical properties of a compound itself, but also has a profound effect on the surrounding molecules. In this paper, we review our recent developments of the methods for predicting the Ka, the equilibrium constant for protonation reactions or acid dissociation reactions. The pKa, which is a logarithm of Ka, is proportional to the reaction Gibbs energy of the protonation reaction, and the reaction free energy can be determined by electronic structure calculations with solvation models. The charge of the compound changes before and after protonation; therefore, the solvent effect plays an important role in determining the reaction Gibbs energy. Here, we review two solvation models: the continuum model, and the integral equation theory of molecular liquids. Furthermore, the reaction Gibbs energy calculations for the protonation reactions require special attention to the handling of dissociated protons. An efficient method for handling the free energy of dissociated protons will also be reviewed.

Synergetic effect of the surface ligand and SiO2 driven photoluminescence stabilization of the CH3NH3PbBr3 perovskite magic-sized clusters

Zero-dimensional Perovskite Magic-size Clusters play crucial roles in understanding and controlling nucleation and growth of semiconductor nanoparticles. However, their metastability behavior is a critical hindrance for reliable characterizations. Here, we report the first demonstration of using an excess amount of surface ligand and SiO2 as novel passivation for synthesizing the magic-sized clusters (MSCs) by the Ligand-assisted reprecipitation method. A synergetic effect between an excessed surface ligand and SiO2 inhibits the protonation and deprotonation reaction between amine-based and acid-based ligand, leading to enhanced PL stability. The obtained CH3NH3PbBr3 PMSCs/SiO2 retain 70% of its initial emission intensity in ambient conditions for 20 days. This passivation approach opens an entirely new avenue for the reliable characterizations of CH3NH3PbBr3 PMSCs, which will significantly broaden their application for understanding and controlling nucleation and growth of semiconductor nanoparticles.

Quantum-Chemical Search for Keto Tautomers of Azulenols in Vacuo and Aqueous Solution

Keto-enol prototropic conversions for carbonyl compounds and phenols have been extensively studied, and many interesting review articles and even books appeared in the last 50 years. Quite a different situation takes place for derivatives of biologically active azulene, for which only scanty information on this phenomenon can be found in the literature. In this work, quantum-chemical studies have been undertaken for symmetrically and unsymmetrically substituted azulenols (constitutional isomers of naphthols). Stabilities of two enol (OH) rotamers and all possible keto (CH) tautomers have been analyzed in the gas phase {DFT(B3LYP)/6-311+G(d,p)} and also in aqueous solution {PCM(water)//DFT(B3LYP)/6-311+G(d,p)}. Contrary to naphthols, for which the keto forms can be neglected, at least one keto isomer (C1H, C2H, and/or C3H) contributes significantly to the tautomeric mixture of each azulenol to a higher degree in vacuo (non-polar environment) than in water (polar amphoteric solvent). The highest amounts of the CH forms have been found for 2- and 5-hydroxyazulenes, and the smallest ones for 1- and 6-hydroxy derivatives. The keto tautomer(s), together with the enol rotamers, can also participate in deprotonation reaction leading to a common anion and influence its acid-base properties. The strongest acidity in vacuo exhibits 6-hydroxyazulene, and the weakest one displays 1-hydroxyazulene, but all azulenols are stronger acids than phenol and naphthols. Bond length alternation in all DFT-optimized structures has been measured using the harmonic oscillator model of electron delocalization (HOMED) index. Generally, the HOMED values decrease for the keto tautomers, particularly for the ring containing the labile proton. Even for the keto tautomers possessing energetic parameters close to those of the enol isomers, the HOMED indices are low. However, some kind of parallelism exists for the keto forms between their relative energies and HOMEDs estimated for the entire molecules.

Nanoporous gold electrodes modified with self-assembled monolayers for electrochemical control of the surface charge

Nanoporous gold is modified with self-assembled monolayers (SAMs) of different length. The point of zero charge and the protonation/deprotonation reaction are investigated revealing precise charge control for long-chain SAMs.

Directed B–H functionalization of the closo-dodecaborate cluster via concerted iodination–deprotonation: reaction mechanism and origins of regioselectivity

A concerted iodination–deprotonation process was discovered for the B–H bond iodination of closo-dodecaborate cluster, which is responsible for the regioselectivity of ortho-B–H functionalization.

LFER and the Effect of Temperature on Oxyanion Adsorption by Goethite

A linear relationship between the Gibbs free energy, ΔGr,H+, of the aqueous complex deprotonation reaction, and the Gibbs free energy, ΔGr,ads, of bidentate surface complexation reaction of oxyanions was derived from modelling of temperature dependent batch equilibrium adsorption experiments. As exemplified in this study, this relationship may be exploited to predict temperature-dependent adsorption behavior of oxyanions not yet known such as pertechnetate.