University of Oulu

Štěpánek, P., & Coriani, S. (2019). Spatial localization in nuclear spin-induced circular dichroism – a quadratic response function analysis. Physical Chemistry Chemical Physics, 21(33), 18082–18091.

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

Saved in:
Author: Štěpánek, Petr1; Coriani, Sonia2
Organizations: 1NMR Research Unit, Faculty of Science, University of Oulu, PO Box 3000, FI-90014 Oulu, Finland
2DTU Chemistry – Department of Chemistry, Technical University of Denmark, 2800 Kgs. Lyngby, Denmark
Format: article
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 5.8 MB)
Persistent link:
Language: English
Published: Royal Society of Chemistry, 2019
Publish Date: 2019-08-26


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.

see all

Series: PCCP. Physical chemistry chemical physics
ISSN: 1463-9076
ISSN-E: 1463-9084
ISSN-L: 1463-9076
Volume: 21
Issue: 33
Pages: 18082 - 18091
DOI: 10.1039/C9CP01716J
Type of Publication: A1 Journal article – refereed
Field of Science: 114 Physical sciences
116 Chemical sciences
Funding: This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement NMOSPEC, No. 654967 (P. Š.) and ETN COSINE, No. 765739 (S. C.). We also thank the Magnus Ehrnrooth Foundation for financial support (P. Š.). The authors acknowledge financial support from the Kvantum institute (University of Oulu) and from Academy of Finland (Grant 316180) (P. Š.). We acknowledge grants of computer capacity from the Finnish Grid and Cloud Infrastructure (persistent identifier urn:nbn:fi:research-infras-2016072533). S. C. acknowledges support from DTU Chemistry and from the Independent Research Fund Denmark – DFF-Forskningsprojekt2 grant no. 7014-00258B.
EU Grant Number: (654967) NMOSPEC - Experimental Nuclear Magneto-Optic Spectroscopy
Academy of Finland Grant Number: 316180
Detailed Information: 316180 (Academy of Finland Funding decision)
Dataset Reference: Supplementary information:
Copyright information: This journal is © the Owner Societies 2019. This Open Access Article is licensed under a Creative Commons Attribution 3.0 Unported Licence.