Calculation of ground and excited state polarizabilities of unsubstituted and donor/acceptor polyenes: A comparison of the finite-field and sum-over-states methods

Citation
Sa. Locknar et al., Calculation of ground and excited state polarizabilities of unsubstituted and donor/acceptor polyenes: A comparison of the finite-field and sum-over-states methods, J PHYS CH A, 103(14), 1999, pp. 2197-2201
Citations number
57
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF PHYSICAL CHEMISTRY A
ISSN journal
10895639 → ACNP
Volume
103
Issue
14
Year of publication
1999
Pages
2197 - 2201
Database
ISI
SICI code
1089-5639(19990408)103:14<2197:COGAES>2.0.ZU;2-0
Abstract
In this manuscript, a relatively simple and inexpensive INDO/SCI finite-fie ld (FF) method for calculating polarizabilities (alpha) is demonstrated to give good agreement with results obtained by both the INDO/MRD/SDCI sum-ove r-states routine and published results using the RPA method. The FF method is as effective as the other techniques in predicting both ground and excit ed state alpha's in all substituted and unsubstituted polyenes studied. We observe the correlation described by Marder and co-workers between bond-ord er-alternation (BOA) and dipolar properties, such as the change in alpha be tween the ground and excited states (Delta alpha). In addition, qualitative , but not quantitative, agreement is seen between the calculated Delta alph a's of polar polyenes and those measured by Stark-effect spectroscopy.