Temperature and external fields in conceptual density functional theory
Marco Franco‐Pérez, Farnaz Heidar‐Zadeh, Paul W. Ayers, Frank De Proft, Alberto Vela, José L. Gázquez, Paul Geerlings
Abstract
denotes the "field". Response functions to changes in the field can then be defined in analogy to classical thermodynamics. The electric field results display a case of a field-induced selectivity in a reaction channel of the Fukui function. Remarkably, atomic electronegativity and hardness in magnetic fields display a piecewise behavior in magnetic fields, associated to configurational jumps upon increasing field strength. The overall compression of their ranges for stronger fields may be insightful when investigating chemistry in extremely high fields. The electronegativity and hardness of diatomics under mechanical force can be traced back to changes in equilibrium distances in the neutral, cationic and anionic state, parallel with the evolution of an intrinsic atomic volume under pressure.