Exploring Chemical Space with the Alchemical Derivatives

Abstract

In this paper, we verify the usefulness of the alchemical derivatives in the prediction of chemical properties. We concentrate on the stability of the transmutation products, where the term "transmutation" means the change of the nuclear charge at an atomic site at constant number of electrons. As illustrative transmutations showing the potential of the method in exploring chemical space, we present some examples of increasing complexity starting with the deprotonation, continuing with the transmutation of the nitrogen molecule, and ending with the substitution of isoelectronic B-N units for C-C units and N units for C-H units in carbocyclic systems. The basis set influence on the qualitative and quantitative accuracies of the alchemical predictions was investigated. The alchemical deprotonation energy (from the second order Taylor expansion) correlates well with the vertical deprotonation energy and can be used as a preliminary indicator for the experimental deprotonation energy. The results of calculations for the BN derivatives of benzene and pyrene show that this method has great potential for efficient and accurate scanning of chemical space.

h function: A protonic take on the numerical Fukui function as a graphical descriptor for deprotonation

“…This would make it an alchemical derivative, which have been used to explore the energy response with respect to a change in nuclear charge in previous theoretical studies. [12][13][14][15][16][17][18] Furthermore, some early efforts to characterize the information that the h function carries, along with calculations for a couple of commonly…”

Atoms in Molecules from Alchemical Perturbation Density Functional Theory

“…Second and higher order alchemical estimates were studied in Refs. [27,[47][48][49][50][51]. Insertion of µ I in Eq.…”

Guiding ab initio calculations by alchemical derivatives

“…12 Alchemical transformations have been used successfully to describe the energy landscape of several molecular compounds. [13][14][15][16] Sheppard et al have shown that the alchemical potential can also be used to predict binding energies of oxygen to a Pd-Rh-Ag nanocluster from the simple calculation of a Pd nanocluster. 17,18 However, only combinations of alchemical transformations have been considered with fixed geometry before and after transformation.…”