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. https://doi.org/10.1039/c9cp01716j
Spatial localization in nuclear spin-induced circular dichroism – a quadratic response function analysis
|Author:||Štěpánek, Petr1; Coriani, Sonia2|
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
|Online Access:||PDF Full Text (PDF, 5.8 MB)|
|Persistent link:|| http://urn.fi/urn:nbn:fi-fe2019082625558
Royal Society of Chemistry,
|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.
PCCP. Physical chemistry chemical physics
|Pages:||18082 - 18091|
|Type of Publication:||
A1 Journal article – refereed
|Field of Science:||
114 Physical sciences
116 Chemical sciences
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 (Academy of Finland Funding decision)
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