University of Oulu

Štěpánek, P. (2020) Nuclear spin-induced optical rotation of functional groups in hydrocarbons. Physical Chemistry Chemical Physics, 22(39), 22195-22206.

Nuclear spin-induced optical rotation of functional groups in hydrocarbons

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Author: Štěpánek, Petr1
Organizations: 1NMR Research Unit, Faculty of Science, University of Oulu, P.O. Box 3000, Oulu, Finland
Format: article
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 4 MB)
Persistent link:
Language: English
Published: Royal Society of Chemistry, 2020
Publish Date: 2020-10-27


Nuclear spin-induced optical rotation (NSOR) is a nuclear magneto-optic effect manifesting as a rotation of the plane of polarization of linearly polarized light induced by nuclear magnetic moments within a molecule. NSOR probes molecular optical properties through localized nuclear interactions and has potential to be developed into a new spectroscopic tool. However, so far the connection between the molecular structure and NSOR response has not been systematically investigated. To obtain insight into this relation and to assess its viability as a foundation for a new spectroscopic method, NSOR of ¹H and ¹³C nuclei in a set of hydrocarbon molecules with various structural motifs is theoretically investigated using density functional theory calculations. The results reveal that NSOR intensities are correlated with several structural features of the molecules, such as the position of the nucleus in the carbon chain, isomerism and presence of nearby unsaturated groups. Specific patterns connecting NSOR to the local chemical environment of the nucleus can be observed. It is also shown that this effect can be to a good approximation modelled as a sum of individual contributions from nearby chemical groups, allowing for a rapid estimation of its values. The demonstrated systematic dependence of the NSOR signal on the molecular structure is a desirable feature for theoretical and experimental development of new spectroscopic methods based on this phenomenon.

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Series: PCCP. Physical chemistry chemical physics
ISSN: 1463-9076
ISSN-E: 1463-9084
ISSN-L: 1463-9076
Volume: 22
Issue: 39
Pages: 22195 - 22206
DOI: 10.1039/D0CP02856H
Type of Publication: A1 Journal article – refereed
Field of Science: 114 Physical sciences
116 Chemical sciences
Funding: The author is grateful for the financial support from Academy of Finland (Grant 316180). The support from the Kvantum institute (University of Oulu) and grants of computer capacity from the Finnish Grid and Cloud Infrastructure (persistent identifier urn:nbn:fi:research-infras-2016072533) are also acknowledged.
Academy of Finland Grant Number: 316180
Detailed Information: 316180 (Academy of Finland Funding decision)
Dataset Reference: Electronic supplementary information (ESI) available: List of molecules, basis set benchmark, additional figures discussing the effects of molecular conformation, isomerism and solvent on the NSOR signal. See DOI: 10.1039/d0cp02856h
Copyright information: © The Author. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.