Premium
Concept of charge transfer: Investigation of charge transfer in the glyoxal–formamide, water dimer, and water–lithium cation systems
Author(s) -
Otto P.,
Ladik J.
Publication year - 1980
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.560180503
Subject(s) - chemistry , supermolecule , water dimer , charge (physics) , population , mulliken population analysis , computational chemistry , dimer , molecule , chemical physics , atomic physics , physics , quantum mechanics , density functional theory , hydrogen bond , organic chemistry , demography , sociology
In this paper an attempt is made to define charge transfer trying also other ways than Mulliken's population analysis. To illustrate this the amount of transferred charge ( q ) in the complexes HCONH 2 + OHC—CHO in two relative geometrical positions, H 2 O + H 2 O and H 2 O + Li + has been calculated with the help of Mulliken's population analysis using the wave function of the complex on the one hand and in the framework of different methods to subdivide the total space of the complex into subspaces for the acceptor and donor molecule, respectively, on the other hand. The results obtained show that Mulliken's population analysis gives a qualitatively correct description of the charge transfer process but to obtain the finer details most probably the use of a single number ( q ) is not sufficient. Further, the change in the total energy with respect to an effective charge transfer of a water dimer and of a solvent–cation complex has been investigated using the new mutually consistent field method. In this way the amount of transferred charge as well as the charge transfer interaction energy have been obtained in one step. These results have been compared with calculations applying second‐order perturbation theory including overlap and the supermolecule method.