Why Bindschedler's Green is redder than Michler's Hydrol Blue

Olsen, Seth (2013) Why Bindschedler's Green is redder than Michler's Hydrol Blue. Journal of Physical Chemistry A, 117 12: 2455-2468. doi:10.1021/jp309006e

Author Olsen, Seth
Title Why Bindschedler's Green is redder than Michler's Hydrol Blue
Journal name Journal of Physical Chemistry A   Check publisher's open access policy
ISSN 1089-5639
Publication date 2013-03-28
Year available 2013
Sub-type Article (original research)
DOI 10.1021/jp309006e
Volume 117
Issue 12
Start page 2455
End page 2468
Total pages 14
Place of publication Washington, DC, United States
Publisher American Chemical Society
Collection year 2014
Language eng
Formatted abstract
We offer a new physical interpretation of the color shift between diarylmethane dyes and their azomethine analogues. We use an isolobal analogy between state-averaged complete active space self-consistent field solutions for corresponding methines and azomethines to show that the shift contains a significant contribution from configuration interaction between a methine-like ππ* excitation and an nπ* excitation out of the azomethine lone pair. The latter does not exist in the corresponding methine systems. This picture is qualitatively inconsistent with traditional models of the shift based on molecular orbital perturbation theory of independent π-electron Hamiltonians. A key prediction is the existence of a dipole-allowed band in the blue/near-UV spectra of the azomethines, which has polarization parallel to the lowest energy band. This forces a revision of past assumptions about the nature of the low-energy spectra of the azomethines. A band at the predicted energies has been observed in solution-state spectra.
Keyword Electronic absorption spectra
Essential-state model
Cationic diarylmethanes
Perturbation theory
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: School of Mathematics and Physics
Official 2014 Collection
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Citation counts: TR Web of Science Citation Count  Cited 4 times in Thomson Reuters Web of Science Article | Citations
Scopus Citation Count Cited 4 times in Scopus Article | Citations
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