Theoretical Investigation of the Mechanism and Dynamics of Intramolecular Coherent Resonance Energy Transfer in Soft Molecules: A Case Study of Dithia-anthracenophane.
A computational study is conducted on dithia-anthracenophane (DTA), for which there is experimental evidence for coherent resonance energy transfer dynamics, and on dimethylanthracene (DMA), a molecule representing the energy donor and the acceptor in DTA. Electronic excitation energies are calculat...
| Publicado en: | Journal of the American Chemical Society Vol. 132; no. 47; pp. 16911 - 16922 |
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| Autores principales: | , , , |
| Formato: | Artículo |
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American Chemical Society
12/1/2010
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| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=55732475&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 55732475 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 12/1/2010 vid: 132 iid: 47 pid: 997 pub: American Chemical Society artinfo: ui: 55732475 10.1021/ja103303u ppf: 16911 ppct: 11 formats: tig: atl: Theoretical Investigation of the Mechanism and Dynamics of Intramolecular Coherent Resonance Energy Transfer in Soft Molecules: A Case Study of Dithia-anthracenophane. aug: au: Lei Yang Caprasecca, Stefano Mennucci, Benedetta Seogjoo Jang affil: Department of Chemistry and Biochemistry, Queens College of the City University of New York, 65-30 Kissena Boulevard, Flushing, New York 11367, United States Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via Risorgimento 35, 56126 Pisa, Italy su: Case studies Energy transfer Resonance Molecules Electronic excitation Density functionals Anthracenophanes sug: subj: Case studies Energy transfer Resonance Molecules Electronic excitation Density functionals Anthracenophanes ab: A computational study is conducted on dithia-anthracenophane (DTA), for which there is experimental evidence for coherent resonance energy transfer dynamics, and on dimethylanthracene (DMA), a molecule representing the energy donor and the acceptor in DTA. Electronic excitation energies are calculated by configuration interaction singles (CIS) and time-dependent density functional theory (TD-DFT) methods and are compared to experimental ones. Electronic coupling constants are calculated between two DMAs embedded into the ground-state structure of DTA employing methods based on transition densities. The resulting values of electronic coupling provide a more consistent interpretation of experiments than those based on one-half the level spacing of DTA excitation energies. Solvation effects are studied based on the polarizable continuum model (PCM). Solvent-induced polarization and screening effects are shown to make opposite contributions, and the net electronic coupling is little different from the value in a vacuum. The likelihood of coherent population transfer is assessed on the basis of a recently developed theory of coherent resonance energy transfer. The time scale of bath is shown to have an important role in sustaining the quantum coherence. The combination of quantum chemical and dynamical data suggests that the electronic coupling in DTA is in the range of 50-100 cm. The presence of oscillatory excitation population dynamics can be understood from the picture of polaronic excitation moderately dressed with dispersive vibrational modes. The effect of torsional modulation on the excitation energies of DTA and electronic coupling is examined on the basis of optimized structures with the torsional angle constrained. The result suggests that inelastic effect due to torsional motion cannot be disregarded in DTA. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2010 holdings: @attributes: islocal: N |
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