Computing the Fukui Function in Solid-State Chemistry: Application to Alkaline Earth Oxides Bulk and Surfaces

Abstract

Fukui functions (FF) are chemical descriptors useful to explain the reactivity of systems towards electron transfer. Whereas they have been widely employed for molecules, their application to extended systems is scarce. One of the reasons for the limited devel-1 opment of such analysis in solids is the improper evaluation of FF in the usual computational approaches based on density functional theory and periodic boundary conditions.In this work we compare the available approaches and propose a new method, based on the interpolation of partially charged systems, that mitigates some of the problems encountered. We discuss the reactivity of alkaline earth oxides (MgO, CaO, SrO and BaO) in terms of the FF analysis, providing a robust way to account for the higher reactivity of surface oxygen sites compared to bulk sites.

Reactivity of Single Transition Metal Atoms on a Hydroxylated Amorphous Silica Surface: A Periodic Conceptual DFT Investigation

“…As such, the introduction or withdrawal of an electron induces an artificial undesired Coulomb interaction between the charged cell and successive reciprocal cells due to its periodicity. Despite the introduction of a first‐order term [60] that allows the total energy of the charged system to be corrected for background charge, Cardenas et al [61] . suggested that the influence of this electrostatic interaction is expected to be significant for systems with pronounced local density of states around the Fermi level, as appears to be the case for the described d‐transition metals.…”

“…These inconsistencies can probably be attributed to the finite difference approximation, which, despite its frequentu se ford escribing the reactivity of atoms and molecules, displays some shortcomings for periodic systems. As such, the introductiono rw ithdrawal of an electron induces an artificial undesired Coulomb interaction between the charged cell and successive reciprocal cells due to its periodicity.D espite the introductiono fafirst-order term [60] that allows the total energy of the charged system to be corrected for background charge, Cardenas et al [61] suggested that the influence of this electrostatic interaction is expected to be significant for systemsw ith pronouncedl ocal density of states around the Fermi level, as appears to be the case for the described d-transition metals. Ap ossible way to attenuate the influence of this interaction consists of using af ractional electron transfer in order to reduce the introduced charge.…”

“…The same analysis can be done for the local softness s r ðÞ . [43,61] The local softness is defined as:…”

Calculation of the Electronic Properties and Reactivity of Nanoribbons

“…Although there is scarcely literature on this topic, a very useful reference for the numerical calculation of the condensed Ffs in periodic boundary conditions within the DFT applied to oxide bulk and surfaces is found here. [49] One qualitative way to obtain Ffs for delocalized periodic systems, such as, the carbon nanoribbons is to extract its electron density and evaluate it by using the Eq. (7) and (8) respectively.…”

Kick–Fukui: A Fukui Function-Guided Method for Molecular Structure Prediction

“…Phenomenologically, chemical reactivity is related to the susceptibility of molecules to transform (react), and its study is a foundational activity in chemistry. Conceptual density functional theory (CDFT) − allows to study chemical reactivity using “response functions” of both electron energy and electron density. ,, In its more than 30 years of history, CDFT has been extensively used to study several reactions, with an interest both in the fundamentals of chemistry (e.g., pericyclic reactions) and in potential applications (e.g., toxicology, biology, catalysis, and material characterization). − However, these studies focus on interpreting and understanding experimentally characterized reactions. To the best of our understanding, CDFT is still being developed to become a predictive tool to guide molecular design, as was the case with molecular orbital-based models, i.e., Woodward and Hoffman rules for predicting the stereochemistry of pericyclic reactions based on orbital symmetry. − Recently, Geerlings et al outlined this shortcoming of CDFT through the question, “Can we move from interpretation to prediction?” …”