Orbitals rigorously defined on molecular fragments, like the extremely localized molecular orbitals, represent a possible way to build up the electronic structure of large molecules, using molecular fragments assembled on small molecules. Of course a rigorous localization is strictly connected to a reduction in the number of variational parameters, which reflects itself in an increased value of the associated energy. In order to get a more accurate description of the target molecule, we have developed a method which allows a relaxation of the electronic structure based on transferred localized orbitals. The relaxation is realized by means of a valence bond technique, which in turn uses the localized nature of the orbitals to reduce the number of excitations. Applications to the transferability of extremely localized molecular orbitals are presented.
|Titolo:||A novel approach to relax extremely localized molecular orbitals: the extremely localized molecular orbital-valence bond method|
|Parole Chiave:||Extremely localized molecular orbitals; Transferability; Valence bond approaches|
|Settore Scientifico Disciplinare:||Settore CHIM/02 - Chimica Fisica|
|Data di pubblicazione:||2004|
|Digital Object Identifier (DOI):||10.1007/s00214-004-0585-0|
|Appare nelle tipologie:||01 - Articolo su periodico|