𝔖 Bobbio Scriptorium
✦   LIBER   ✦

Optimal virtual orbitals to relax wave functions built up with transferred extremely localized molecular orbitals

✍ Scribed by Alessandro Genoni; Arianna Fornili; Maurizio Sironi


Publisher
John Wiley and Sons
Year
2005
Tongue
English
Weight
182 KB
Volume
26
Category
Article
ISSN
0192-8651

No coin nor oath required. For personal study only.

✦ Synopsis


Abstract

Extremely localized molecular orbitals (ELMOs), namely orbitals strictly localized on molecular fragments, are easily transferable from one molecule to another one. Hence, they provide a natural way to set up the electronic structure of large molecules using a data base of orbitals obtained from model molecules. However, this procedure obviously increases the energy with respect to a traditional MO calculation. To gain accuracy, it is important to introduce a partial electron delocalization. This can be carried out by defining proper optimal virtual orbitals that supply an efficient set for nonorthogonal configurations to be employed in VB‐like expansions. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 827–835, 2005