Premium
New insights in conceptual DFT: New model for the calculation of local reactivity indices based on the Sanderson's principle
Author(s) -
SánchezMárquez Jesús,
García Víctor,
Zorrilla David,
Fernández Manuel
Publication year - 2019
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25844
Subject(s) - reactivity (psychology) , ambiguity , statistical physics , fukui function , computational chemistry , set (abstract data type) , atom (system on chip) , electrophile , theoretical physics , chemistry , physics , computer science , medicine , biochemistry , alternative medicine , pathology , embedded system , programming language , catalysis
Abstract In the present study, a new model mainly based on the Sanderson's principle for estimating important reactivity descriptors, such as the local hardness and the local electrophilicity, is introduced. New approximations and corrections were taken into account, which led to a significantly different development, obtaining more realistic results than the previous ones used. The Fukui condensed‐to‐atom indices: f − and f + have been used in this model, but their role is clearly described in the development, reducing therefore, the ambiguity of previous developments where the indices could be arbitrarily used. It is important to underline that the proposed model is relatively simple , but leads to qualitatively correct results. It also makes it possible to interpret the hard‐soft acid base principle in local terms, as can be seen in the sample set of reactions (Diels‐Alder type) selected as an example in the present study, and which provides very coherent results with the expected experimental reactivity.