Nogueira2017.pdf (876.42 kB)
Electronic delocalization, charge transfer and hypochromism in the UV absorption spectrum of polyadenine unravelled by multiscale computations and quantitative wavefunction analysis
journal contribution
posted on 2018-03-06, 11:42 authored by Juan J. Nogueira, Felix PlasserFelix Plasser, Leticia Gonzalez© 2017 The Royal Society of Chemistry. The characterization of the electronically excited states of DNA strands populated upon solar UV light absorption is essential to unveil light-induced DNA damage and repair processes. We report a comprehensive analysis of the electronic properties of the UV spectrum of single-stranded polyadenine based on theoretical calculations that include excitations over eight nucleobases of the DNA strand and environmental effects by a multiscale quantum mechanics/molecular mechanics scheme, conformational sampling by molecular dynamics, and a meaningful interpretation of the electronic structure by quantitative wavefunction analysis. We show that electronic excitations are extended mainly over two nucleobases with additional important contributions of monomer-like excitations and excitons delocalized over three monomers. Half of the spectral intensity derives from locally excited and Frenkel exciton states, while states with partial charge-transfer character account for the other half and pure charge-transfer states represent only a minor contribution. The hypochromism observed when going from the isolated monomer to the strand occurs independently from delocalization and charge transfer and is instead explained by long-range environmental perturbations of the monomer states.
Funding
This material is based upon work supported by the VSC Research Center funded by the Austrian Federal Ministry of Science, Research and Economy (bmwfw).
History
School
- Science
Department
- Chemistry
Published in
Chemical ScienceVolume
8Issue
8Pages
5682 - 5691Citation
NOGUEIRA, J.J., PLASSER, F. and GONZALEZ, L., 2017. Electronic delocalization, charge transfer and hypochromism in the UV absorption spectrum of polyadenine unravelled by multiscale computations and quantitative wavefunction analysis. Chemical Science, 8(8), pp. 5682-5691.Publisher
© Royal Society of ChemistryVersion
- VoR (Version of Record)
Publisher statement
This work is made available according to the conditions of the Creative Commons Attribution-NonCommercial 3.0 Unported (CC BY-NC 3.0) licence. Full details of this licence are available at: http://creativecommons.org/licenses/by-nc/3.0/Acceptance date
2017-06-09Publication date
2017-06-13Copyright date
2017Notes
This is an Open Access Article. It is published by royal Society of Chemistry under the Creative Commons Attribution-NonCommercial 3.0 Unported (CC BY-NC). Full details of this licence are available at: http://creativecommons.org/licenses/by-nc/3.0/ISSN
2041-6520eISSN
2041-6539Publisher version
Language
- en