Premium
On the redistribution of electrons for chemical reaction systems
Author(s) -
Tachibana Akitomo,
Parr Robert G.
Publication year - 1992
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.560410402
Subject(s) - excitation , hsab theory , redistribution (election) , transferability , electron transfer , electron , chemistry , density functional theory , reaction coordinate , chemical physics , atomic physics , electron density , computational chemistry , physics , quantum mechanics , mathematics , statistics , logit , law , politics , political science
A regional density‐functional theory is formulated and applied to the study of ground‐state electron redistributions during the course of a chemical reaction. If for a given increment of the reaction process, accumulation of electrons occurs in a certain region of space, then it is called the dynamic acceptor region, denoted by P . The complement is called the dynamic donor region, denoted by Q . The regional energy itself is determined as a unique functional of the electron density of the total system. The regional transfer potentials are defined in such a way that they add to give the total chemical potential, and their values along the reaction coordinate are found to be different between P and Q . The difference between the regional transfer potentials is shown to provide the driving force for electron transfer from Q to P . A characteristic coordinate for following electron transfer and an associated excitation potential are introduced. The excitation potential is a measure of regional virtual excitation due to regional interactions. The regional transfer potential gives the local character of electron transferability, while the excitation potential gives the global character. The theory encompasses the concepts of regional hardness and softness and sheds light on the HSAB principle.