A Time‐Dependent Density Functional Theory Investigation on the Origin of Red Chemiluminescence |
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| Authors: | Chun‐Gang Min Ai‐Min Ren Prof Jing‐Fu Guo Prof Zhong‐Wei Li Lu‐Yi Zou Dr John D Goddard Prof Ji‐Kang Feng Prof |
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| Institution: | 1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun (P. R. China), Fax: (+86)?0431‐88945942;2. School of Physics, Northeast Normal University, Changchun (P. R. China);3. Department of Chemistry, University of Guelph, Guelph, Ontario (Canada) |
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| Abstract: | Is the resonance‐based anionic keto form of oxyluciferin the chemical origin of multicolor bioluminescence? Can it modulate green into red luminescence? There is as yet no definitive answer from experiment or theory. The resonance‐based anionic keto forms of oxyluciferin have been proposed as a cause of multicolor bioluminescence in the firefly. We model the possible structures by adding sodium or ammonium cations and investigating the ground‐ and excited‐state geometries as well as the electronic absorption and emission spectra. A role for the resonance structures is obvious in the gas phase. The absorption and emission spectra of the two structures are quite different—one in the blue and another in the red. The differences in the spectra of the models are small in aqueous solution, with all the absorption and emission spectra in the yellow–green region. The resonance‐based anionic keto form of oxyluciferin may be one origin of the red‐shifted luminescence but is not the exclusive explanation for the variation from green (≈530 nm) to red (≈635 nm). We study the geometries, absorption, and emission spectra of the possible protonated compounds of keto(?1) in the excited states. A new emitter keto(?1)′‐H is considered. |
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| Keywords: | computational chemistry density functional calculations luminescence protonated compounds resonance structures |
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