Premium
Chemical fragments in real space: Definitions, properties, and energetic decompositions
Author(s) -
Pendás A. Martín,
Blanco M. A.,
Francisco E.
Publication year - 2006
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20469
Subject(s) - density matrix , statistical physics , partition (number theory) , chemistry , formalism (music) , atomic charge , quantum chemical , redistribution (election) , quantum , charge density , fuzzy logic , quantum mechanics , computational chemistry , theoretical physics , physics , mathematics , molecule , computer science , combinatorics , art , musical , politics , political science , law , visual arts , artificial intelligence
The physical and chemical meaning of real space molecular fragments resulting from arbitrary partitions of the density is reviewed under a common unifying formalism. Both fuzzy (interpenetrating) and non‐fuzzy (exhaustive) decompositions are treated on an equal basis. Density decompositions are consistently generalized to compatible density matrix partitions by using Li and Parr's ideas (Li and Parr J Chem Phys 1986, 84, 1704), and these are carried onto an energy partition. It is argued that the merits of a given decomposition should be judged against both the charge and the energetic image it provides. Atomic partitions are used to show how the interacting quantum atoms approach (IQA) allows us to cope with the most important energy cancellations of quantum chemistry. Binding results from a trade‐off between atomic (or fragment) energy deformations with respect to a reference and interatomic (interfragment) interactions. Deformation energies are divided into charge transfer and redistribution terms and their relative roles are analyzed. A number of systems are compared against the fuzziness of different density decompositions. The results consistently show that fuzzy partitions tend to give low atomic net charges and enhanced covalency, while exhaustive partitions generate larger net charges and smaller covalencies, across a wide range of bonding regimes. © 2006 Wiley Periodicals, Inc. J Comput Chem, 2007