External fields in conceptual density functional theory

Abstract

The necessity of the recent incorporation of new external variables in the context of conceptual DFT (CDFT) is discussed based on the ever‐increasing portfolio of experimental reaction conditions in the endeavor of experimentalists to synthesize new molecules with unprecedented properties. Electric and magnetic fields (ε and B), mechanical forces (F), and confinement are proposed as valuable new variables, extending conventional CDFT and its associated response functions. A finite field approach is used to calculate the evolution of both global and local descriptors in a selected series of atomic and molecular applications, and from it derive new response function involving, with one exception, the first derivative to the field considered. The electric field results, displaying, for example, a case of a field‐induced enantioselectivity in the Fukui function, may be instrumental in the recent upsurge of chemistry in oriented external electric fields. The study of atomic electronegativity and hardness in magnetic fields displays a piecewise behavior, associated to configurational jumps upon increasing field strength and reveals an overall compression of their ranges for stronger fields, which may be guiding upon investigating chemistry in extremely high fields like in white dwarfs. The evolution of the electronegativity and hardness of diatomics under mechanical force can elegantly be traced back to differences in their equilibrium distance in the neutral, cationic, and anionic state. The well‐known reduction of the polarizability under confinement can be seen as a fore‐runner of the increasing hardness of atoms under pressure, presently under investigation. Periodicity showing up in a spontaneous way in the variety of properties is a leitmotiv in this study, as well as the interconnections/analogies between the different response functions.

Impacts of external fields on aromaticity and acidity of benzoic acid: a density functional theory, conceptual density functional theory and information-theoretic approach study

“…The impact of external fields has attracted considerable research interest in the recent literature. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] It is commonly believed that they can influence the structure, [18][19][20][21] reactivity, [22][23][24][25] and other electronic properties of a molecular system. [26][27][28][29] Earlier, we studied the behavior of chiral molecules in external fields and obtained similar results.…”

Gradient Bundle Analysis of Electric Field Induced Changes in Electron Charge Density

“…CDFT has recently been extended to include the effect of EFs as well as other external factors. , The most relevant first- and second-order response functions including electric fields, ε , are bold-italicμ dip = true( ∂ E ∂ bold-italicε true) N , v ( r ) boldA = true( ∂ 2 E ∂ bold-italicε 2 true) N , v ( r ) ( ∂ ρ false( boldr false) ∂ ε ) = true( ∂ 2 E ∂ ε δ ν ( r ) true) N where μ dip is the dipole vector and A is the polarizability tensor. The quantity given by eq is referred to as the EF-induced density and will be discussed in detail in this work.…”

“…CDFT has recently been extended to include the effect of EFs as well as other external factors. , The most relevant first- and second-order response functions including electric fields, ε , are where μ dip is the dipole vector and A is the polarizability tensor. The quantity given by eq is referred to as the EF-induced density and will be discussed in detail in this work.…”

“…CDFT has recently been extended to include the effect of EFs as well as other external factors. 19,44 The most relevant first-and second-order response functions including electric fields, ε, are i k j j j y…”

Wandering through quantum-mechanochemistry: from concepts to reactivity and switches

“…To put the conceptual aspect in a broader context, it is part of the ALGC research program 35 on the inclusion of external ''fields'' in Conceptual DFT (CDFT), [36][37][38][39][40][41][42][43][44][45][46] for many years one of the central topics of our research. 39,42,44,45 Conceptual DFT is essentially a density-based reactivity theory in which the reactivity of a molecule is described in terms of a series of response functions.…”