Chemical transferability of functional groups follows from the nearsightedness of electronic matter

Proc Natl Acad Sci U S A. 2017 Oct 31;114(44):11633-11638. doi: 10.1073/pnas.1615053114. Epub 2017 Oct 16.

Abstract

We establish the physical origins of chemical transferability from the perspective of the nearsightedness of electronic matter. To do this, we explicitly evaluate the response of electron density to a change in the system, at constant chemical potential, by computing the softness kernel, [Formula: see text] The softness kernel is nearsighted, indicating that under constant-chemical-potential conditions like dilute solutions changing the composition of the molecule at [Formula: see text] has only local effects and does not have any significant impact on the reactivity at positions [Formula: see text] far away from point [Formula: see text] This locality principle elucidates the transferability of functional groups in chemistry.

Keywords: chemical transferability; density functional theory; electronic matter; linear response; nearsightedness.

Publication types

  • Research Support, Non-U.S. Gov't