Abstract
The question of electron localization in isolated molecules and mixed-valence vs. averaged-valence structure is examined both from purely electronic and from vibronic viewpoints. Generally, a four-site model, in which two sites encompass a localization region in the molecule, is useful; the variation of the distance between the two sites in each region provides the vibronic coupling to localize the electrons. In a simple Hückel picture, we derive a closed-form perturbation-theoretic criterion for the stability ot the localized (distorted) geometry; it is favored except for excessively polar structures. Adding the elastic energy of the framework increases the stability of the delocalized (averaged-valence or undistorted) geometry relative to the localized one. We present a diabatic coordinate curve-crossing analysis of the intramolecular electron-transfer problem, which permits straightforward classification of mixed-valent states and transfer processes. The vibronic picture leading to localization is quite similar to that employed in the pseudo-Jahn-Teller effect.
| Original language | English |
|---|---|
| Pages (from-to) | 3265-3271 |
| Number of pages | 7 |
| Journal | Journal of the American Chemical Society |
| Volume | 103 |
| Issue number | 12 |
| Publication status | Published - 1981 |
Fingerprint
ASJC Scopus subject areas
- Chemistry(all)
Cite this
Intramolecular electron delocalization : A four-site model. / Linderberg, Jan; Ratner, Mark A.
In: Journal of the American Chemical Society, Vol. 103, No. 12, 1981, p. 3265-3271.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Intramolecular electron delocalization
T2 - A four-site model
AU - Linderberg, Jan
AU - Ratner, Mark A
PY - 1981
Y1 - 1981
N2 - The question of electron localization in isolated molecules and mixed-valence vs. averaged-valence structure is examined both from purely electronic and from vibronic viewpoints. Generally, a four-site model, in which two sites encompass a localization region in the molecule, is useful; the variation of the distance between the two sites in each region provides the vibronic coupling to localize the electrons. In a simple Hückel picture, we derive a closed-form perturbation-theoretic criterion for the stability ot the localized (distorted) geometry; it is favored except for excessively polar structures. Adding the elastic energy of the framework increases the stability of the delocalized (averaged-valence or undistorted) geometry relative to the localized one. We present a diabatic coordinate curve-crossing analysis of the intramolecular electron-transfer problem, which permits straightforward classification of mixed-valent states and transfer processes. The vibronic picture leading to localization is quite similar to that employed in the pseudo-Jahn-Teller effect.
AB - The question of electron localization in isolated molecules and mixed-valence vs. averaged-valence structure is examined both from purely electronic and from vibronic viewpoints. Generally, a four-site model, in which two sites encompass a localization region in the molecule, is useful; the variation of the distance between the two sites in each region provides the vibronic coupling to localize the electrons. In a simple Hückel picture, we derive a closed-form perturbation-theoretic criterion for the stability ot the localized (distorted) geometry; it is favored except for excessively polar structures. Adding the elastic energy of the framework increases the stability of the delocalized (averaged-valence or undistorted) geometry relative to the localized one. We present a diabatic coordinate curve-crossing analysis of the intramolecular electron-transfer problem, which permits straightforward classification of mixed-valent states and transfer processes. The vibronic picture leading to localization is quite similar to that employed in the pseudo-Jahn-Teller effect.
UR - http://www.scopus.com/inward/record.url?scp=0012744277&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0012744277&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0012744277
VL - 103
SP - 3265
EP - 3271
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 12
ER -