ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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 HCONH2 + OHC - CHO in two relative geometrical positions, H2O + H2O and H2O + 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.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560180503
