Nuclear spin-induced optical rotation of functional groups in hydrocarbons
1NMR Research Unit, Faculty of Science, University of Oulu, P.O. Box 3000, Oulu, Finland
|Online Access:||PDF Full Text (PDF, 4 MB)|
|Persistent link:|| http://urn.fi/urn:nbn:fi-fe2020102787876
Royal Society of Chemistry,
|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.
PCCP. Physical chemistry chemical physics
|Pages:||22195 - 22206|
|Type of Publication:||
A1 Journal article – refereed
|Field of Science:||
114 Physical sciences
116 Chemical sciences
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 (Academy of Finland Funding decision)
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
© The Author. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.