Abstract Using simple functionals of the electron density to appreciate and quantify molecular structure chemical reactivity properties is a recent endeavor in functional theory (DFT) toward development new theory. According first Hohenberg–Kohn theorem DFT, alone should be able determine any property ground state. Exchange correlation energies are such properties, so reactivity, hence they all accurately determined by functionals. Quantities as Shannon entropy, Fisher information,...

Establishing a chemical reactivity theory in density functional (DFT) language has been our intense research interest the past two decades, exemplified by determination of steric effect and stereoselectivity, evaluation electrophilicity nucleophilicity, identification strong weak interactions, formulation cooperativity, frustration, principle chirality hierarchy. In this Featured Article, we first overview four density-based frameworks DFT to appreciate understanding, including conceptual...

Molecular acidity is one of the important physiochemical properties a molecular system, yet its accurate calculation and prediction are still an unresolved problem in literature. In this work, we propose to make use quantities from information‐theoretic (IT) approach density functional reactivity theory provide description completely new perspective. To illustrate our point, five different categories acidic series, singly doubly substituted benzoic acids, benzenesulfinic benzeneseleninic...

A number of strong linear correlations between information-theoretic quantities and electron populations for atoms, molecules, atoms-in-molecules have been disclosed.

To accurately predict the capability and possible reaction site for atoms in molecules to donate or accept electrons chemical processes, i.e., quantitatively determine electrophilicity, nucleophilicity, regioselectivity, is an important yet incomplete task. Earlier, we proposed using Hirshfeld charge information gain as two equivalent descriptors this purpose, based on Information Conservation Principle recently proposed. This idea was successfully applied series of molecular systems confirm...

How to accurately predict electronic properties of a Columbic system with the electron density obtained from experiments such as X-ray crystallography is still an unresolved problem. The information–theoretic approach recently developed in framework functional reactivity theory one efforts address issue. In this work, using 27 atoms and 41 molecules illustrative examples, we present study demonstrate that able satisfactorily describe total energy its components quantities like Shannon...

One of the main tasks theoretical chemistry is to rationalize computational results with chemical insights. Key concepts such nature include nucleophilicity, electrophilicity, regioselectivity, and stereoselectivity. While tools are available predict barrier heights other reactivity properties acceptable accuracy, a conceptual framework appreciate above quantities still lacking. In this work, we introduce electronic force as fundamental driving processes understand molecular reactivity. It...

For a given size of one fullerene molecule, there could exist many different isomers and their energy landscape is remarkably complex. To have better understanding the nature origin isomeric stability, as continuation our previous endeavors, we systematically dissect molecular stability four systems, C44, C48, C52, C60, with total 2547 structures, using density functional theory information-theoretic approach. The decomposition analysis beneficial to understand stability. Our results...

Molecular systems bound together through noncovalent interactions are ubiquitous in nature, many of which involved essential life processes, yet little is known about the principles governing their structure, stability, and function. Cooperativity as one intrinsic properties these plays a key role. In this work, on basis our recent quantification scheme cooperativity effect, we present general pattern to identify positively cooperative negatively cooperative. We show that homogeneous...

Though density functional theory is widely accepted as one of the most successful developments in theoretical chemistry past few decades, knowledge how to apply this new electronic structure theory, help us better understand chemical processes and transformations, still an unaccomplished task. The information-theoretic approach emerging a viable option for that purpose recent literature, providing insights about steric effect, cooperativity, electrophilicity, nucleophilicity,...

To effectively leverage and convert cheap, abundant, environmentally friendly solar energy is still an unaccomplished endeavor. In this work, we prepare characterize the long-lasting red-light-emitting, single-phase Ca2Zn4Ti16O38 phosphor by sol−gel method with nonstoichiometry or addition of H3BO3 as flux. Excitation emission mechanisms are proposed supported computational results from density functional theory. Phase identification powders was performed X-ray powder diffraction analysis,...

Cooperativity is a widely used chemical concept whose existence ubiquitous in and biological systems but quantification still controversial origin much less appreciated. In this work, using the interaction energy of molecular system, which composed multiple copies building block, we propose quantitative measurement to evaluate cooperativity effect. This approach then applied six systems, i.e., water cluster, argon protonated zinc atom cluster on top graphene sheet, alpha helix glycine amino...

As one of the most widely used chemical concepts whose origin can be traced back to Lewis theory bonding a century ago, covalent bond involves sharing or more pairs electrons between atoms. A strong interaction (SCI) is such that two electron are shared, yielding double, triple, quadruple, even higher order. Despite its ubiquity and usefulness, robust generally applicable approach accurately identify interactions determine their orders still lacking. In this work, an SCI index proposed from...

Even though the concept of aromaticity and antiaromaticity is extremely important widely used, there still exist lots controversies in literature, which are believed to be originated from fact that so many aromatic types discovered at same time indexes proposed. In this work, using seven series substituted fulvene derivatives as an example with information-theoretic approach density functional reactivity theory, we examine these concepts a different perspective. We investigate changing...

Examining global and local aromaticity for acenes using an information-theoretic approach indices provides a unique perspective these compounds.

The oxidation state, also called number, of atoms in molecules is a fundamental chemical concept. It defined as the charge an atom molecule after ionic approximation its heteronuclear bonds applied. Even though for simple assignment states straightforward, redundancy and ambiguity do exist others. In this work, we present density-based framework to determine state using quantities from information-theoretic approach. As proof concept, examined six elements total 49 molecules. Strong linear...

Chemical bonds and noncovalent interactions are extraordinarily important concepts in chemistry beyond. Using density-based quantities to describe them has a long history the literature, yet none can satisfactorily entire spectrum of from strong chemical weak van der Waals forces. In this work, employing Pauli energy as theoretical foundation, we fill that knowledge gap. Our results show newly established index single multiple covalent bonds, ionic metallic different kinds interactions, all...

The electrophilic aromatic substitution for nitration, halogenation, sulfonation, and acylation is a vastly important category of chemical transformation. Its reactivity regioselectivity predominantly determined by nucleophilicity carbon atoms on the ring, which in return immensely influenced group that attached to ring priori. In this work, taking advantage recent developments quantifying (electrophilicity) with descriptors from information-theoretic approach density functional theory, we...

The steric effect is one of the most widely used chemical concepts in chemistry, yet a generally accepted implementation its formulation and quantification from theoretical viewpoint, if even possible, still an unaccomplished task. Based on energetics viewpoint our earlier proposal using Weizsäcker kinetic energy as contribution well recent work force reliable local descriptor to account for origin stereoselective propensity reactions, this work, we systematically examine behavior general...