RESUMO
In this paper, we derive a reactivity descriptor stemming from the Fermi-Dirac population scheme, applied to density functional calculations on molecular systems. Assuming that molecular orbitals only marginally change when temperature is slightly increased from 0 K, we study the response of electron density to a change in temperature. Connection with usual conceptual density functional theory descriptors is made, and the T-variation of electron density for some representative examples is given and discussed.
RESUMO
In this publication, we propose a new set of reactivity/selectivity descriptors, derived within a Rayleigh-Schrödinger perturbation theory framework, for chemical systems undergoing an electrostatic (point-charge) perturbation. From the electron density polarization at first order, qualitative insight on reactivity is retrieved, while more quantitative information (noteworthy selectivity) can be obtained from either the second-order energy response or the number of shifted electrons under perturbation. Noteworthily, only a small number of excitations contribute significantly to the overall responses to perturbation, suggesting chemical reactivity could be foreseen by a careful scrutiny of the electron density reorganization upon excitation.
RESUMO
In a recent article Polanco-Ramirez et al. proposed new definitions of local chemical potential and local hardness starting from the first derivative of the energy with respect to the number of electrons and a smart use of the chain rule. In this comment we show that this derivation appears naturally in the Taylor expansion of the energy, showing that the construction of Polanco-Ramirez et al. is not artificially built.
