University of Oulu

Štěpánek, P. et al. Relation between molecular electronic structure and nuclear spin-induced circular dichroism. Sci. Rep. 7, 46617; doi: 10.1038/srep46617 (2017)

Relation between molecular electronic structure and nuclear spin-induced circular dichroism

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Author: Štěpánek, Petr1,2; Coriani, Sonia3; Sundholm, Dage4;
Organizations: 1NMR Research Unit, University of Oulu, PO Box 3000, FI-90014 Oulu, Finland
2Institute of Organic Chemistry and Biochemistry, AS CR, Flemingovo nam. 2, 166 10 Prague, Czech Republic
3DTU Chemistry - Department of Chemistry, Technical University of Denmark, 2800 Kgs. Lyngby, Denmark
4Department of Chemistry, University of Helsinki, FI-00014 Helsinki, Finland
5Emanuel Institute of Biochemical Physics RAS, Kosygin street 4, 119334 Moscow, Russia
Format: article
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 2 MB)
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Language: English
Published: Springer Nature, 2017
Publish Date: 2017-06-30


The recently theoretically described nuclear spin-induced circular dichroism (NSCD) is a promising method for the optical detection of nuclear magnetization. NSCD involves both optical excitations of the molecule and hyperfine interactions and, thus, it offers a means to realize a spectroscopy with spatially localized, high-resolution information. To survey the factors relating the molecular and electronic structure to the NSCD signal, we theoretically investigate NSCD of twenty structures of the four most common nucleic acid bases (adenine, guanine, thymine, cytosine). The NSCD signal correlates with the spatial distribution of the excited states and couplings between them, reflecting changes in molecular structure and conformation. This constitutes a marked difference to the nuclear magnetic resonance (NMR) chemical shift, which only reflects the local molecular structure in the ground electronic state. The calculated NSCD spectra are rationalized by means of changes in the electronic density and by a sum-over-states approach, which allows to identify the contributions of the individual excited states. Two separate contributions to NSCD are identified and their physical origins and relative magnitudes are discussed. The results underline NSCD spectroscopy as a plausible tool with a power for the identification of not only different molecules, but their specific structures as well.

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Series: Scientific reports
ISSN: 2045-2322
ISSN-E: 2045-2322
ISSN-L: 2045-2322
Volume: 7
Article number: 46617
DOI: 10.1038/srep46617
Type of Publication: A1 Journal article – refereed
Field of Science: 114 Physical sciences
116 Chemical sciences
Funding: This work was supported by the Academy of Finland through projects (287791 and 275845, D.S.) and directed program in Computational Science (258565, J.V.). We are grateful for financial support from European Union’s (EU) Horizon 2020 (P.S., MSCA-IF-2014-EF, Grant Number 654967) and the FP7 AIAS-COFUND program (S.C., Grant Agreement No. 609033). P.S. was additionally supported by Czech Science Foundation (grant no. 13-03978S). We acknowledge the Magnus Ehrnrooth Foundation for financial support (D.S., V.O.).
EU Grant Number: (654967) NMOSPEC - Experimental Nuclear Magneto-Optic Spectroscopy
Academy of Finland Grant Number: 258565
Detailed Information: 258565 (Academy of Finland Funding decision)
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