Jump to main content
Jump to site search

Issue 33, 2019
Previous Article Next Article

Spatial localization in nuclear spin-induced circular dichroism – a quadratic response function analysis

Author affiliations

Abstract

Nuclear magneto-optic (NMO) effects are recently described phenomena originating from the interaction of light with local magnetic fields produced by nuclear spins. The phenomena border nuclear magnetic resonance and optical spectroscopy and are expected to provide rather unique spectroscopic features, borrowing from both localized response of the atomic nuclei as well as more global excitation properties of the whole molecule or its chromophore moieties. A number of quantum-chemical computational studies have been carried out, offering a reasonable agreement with nuclear magneto-optics experiments performed so far. However, the detailed structure-spectra relation is still poorly understood. In this report we address the question of locality of one of the NMO effects, namely nuclear spin-induced circular dichroism (NSCD). We implement an alternative computational approach for calculation of the NSCD intensities, based on residues of quadratic response functions, and use it to investigate the NSCD response of different nuclei in a model molecular system with well-defined separate chromophores. The results show that significant NSCD at a given energy only occurs at the nuclei which are located in the chromophore that is excited. We rationalize these findings using analysis via difference densities, and approximate sum-over-states calculations. This behaviour of NSCD opens a way to experimental studies of localization of excited states in molecules, potentially with resolution down to the order of bond-length.

Graphical abstract: Spatial localization in nuclear spin-induced circular dichroism – a quadratic response function analysis

Back to tab navigation

Supplementary files

Publication details

The article was received on 27 Mar 2019, accepted on 18 May 2019 and first published on 20 May 2019


Article type: Paper
DOI: 10.1039/C9CP01716J
Phys. Chem. Chem. Phys., 2019,21, 18082-18091
  • Open access: Creative Commons BY license
  •   Request permissions

    Spatial localization in nuclear spin-induced circular dichroism – a quadratic response function analysis

    P. Štěpánek and S. Coriani, Phys. Chem. Chem. Phys., 2019, 21, 18082
    DOI: 10.1039/C9CP01716J

    This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

    Reproduced material should be attributed as follows:

    • For reproduction of material from NJC:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
    • For reproduction of material from PCCP:
      [Original citation] - Published by the PCCP Owner Societies.
    • For reproduction of material from PPS:
      [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
    • For reproduction of material from all other RSC journals:
      [Original citation] - Published by The Royal Society of Chemistry.

    Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.

Search articles by author

Spotlight

Advertisements