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  Theoretical Study of the Photophysics of 8-Vinylguanine, an Isomorphic Fluorescent Analogue of Guanine

Kochman, M., Pola, M., & Miller, R. J. D. (2016). Theoretical Study of the Photophysics of 8-Vinylguanine, an Isomorphic Fluorescent Analogue of Guanine. The Journal of Physical Chemistry A, 120(31), 6200-6215. doi:10.1021/acs.jpca.6b04723.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-002B-09AF-B Version Permalink: http://hdl.handle.net/11858/00-001M-0000-002B-5005-A
Genre: Journal Article

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http://dx.doi.org/10.1021/acs.jpca.6b04723 (Publisher version)
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 Creators:
Kochman, Michał1, 2, Author              
Pola, Martina1, 2, 3, Author              
Miller, R. J. Dwayne1, 2, 4, Author              
Affiliations:
1Miller Group, Atomically Resolved Dynamics Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society, ou_1938288              
2The Hamburg Centre for Ultrafast Imaging, Luruper Chaussee 149, 22761 Hamburg, Germany, ou_persistent22              
3Institut für Theoretische Physik, Universität Hamburg, Jungiusstraße 9, 20355 Hamburg, Germany, ou_persistent22              
4Department of Chemistry and Physics, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6, Canada., ou_persistent22              

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 Abstract: Paving the way for the application of the algebraic-diagrammatic construction scheme of second order (ADC(2)) to systems based on the guanine chromophore, we demonstrate the this excited-state electronic structure method provides a realistic description of the photochemistry of 9H-guanine, in close agreement with the benchmark provided by the CASPT2 method. We then proceed to apply the ADC(2) method to the photochemistry of 8-vinylguanine (8vG), a minimally modified analogue of guanine which, unlike the naturally occurring nucleobase, displays intense fluorescence, indicative of a much longer-lived excited electronic state. The emissive electronic state of 8vG is identified as an ππ*-type intramolecular charge transfer (ICT) state, in which a charge of roughly −0.2 e is transferred from the guanine moiety onto the vinyl substituent. The main radiationless deactivation pathway competing with fluorescence is expected to involve the molecule leaving the minimum on the ICT ππ* state, and reaching a region of the S1 adiabatic state where it resembles the La ππ* state of unmodified 9H-guanine. The topology of the La ππ* region of the S1 state favors subsequent internal conversion at a crossing seam with the ground electronic state. The sensitivity of this process to environment polarity may explain the experimentally-observed fluorescence quenching of 8vG upon incorporation in single- and double-stranded DNA.

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Language(s): eng - English
 Dates: 2016-05-102016-07-182016-08-11
 Publication Status: Published in print
 Pages: 16
 Publishing info: -
 Table of Contents: -
 Rev. Method: Peer
 Identifiers: DOI: 10.1021/acs.jpca.6b04723
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Title: The Journal of Physical Chemistry A
  Other : J. Phys. Chem. A
Source Genre: Journal
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Publ. Info: Columbus, OH : American Chemical Society
Pages: - Volume / Issue: 120 (31) Sequence Number: - Start / End Page: 6200 - 6215 Identifier: ISSN: 1089-5639
CoNE: /journals/resource/954926947766_4