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Control of delocalization and structural changes by means of an electric field
Author(s) -
Karafiloglou Padeleimon
Publication year - 2006
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20509
Subject(s) - delocalized electron , electric field , polar , field (mathematics) , basis (linear algebra) , electronic structure , electron , physics , atomic physics , materials science , molecular physics , condensed matter physics , geometry , quantum mechanics , mathematics , pure mathematics
The strength and, mainly, the direction of a static electric field can be used to control delocalization effects occurring in a non‐polar π‐system. The delocalization energy, the weights, and the probabilities of some local electronic structures, the behavior of electron pairs, and the electronic fluctuations are considered and examined in cis ‐butadiene, used as model system. The effects of the electric field are detected and evaluated in the basis of natural orbital spaces appropriate to investigate the behavior of one‐ and poly‐electron distributions. The consequences of modifying the delocalization effects on structural changes are also investigated. Full geometry optimizations in both Hartree–Fock and MP2 levels show that the changes in bond lengths, guided by the changes of the behavior of the electronic assembly, can be controlled by means of the electric field. © 2006 Wiley Periodicals, Inc. J Comput Chem, 2006