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Low-frequency Raman optical activity provides insight into the structure of chiral liquids
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SYSNO ASEP 0560563 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Low-frequency Raman optical activity provides insight into the structure of chiral liquids Author(s) Michal, P. (CZ)
Kapitán, J. (CZ)
Kessler, J. (CZ)
Bouř, Petr (UOCHB-X) RID, ORCIDSource Title Physical Chemistry Chemical Physics. - : Royal Society of Chemistry - ISSN 1463-9076
Roč. 24, č. 33 (2022), s. 19722-19733Number of pages 12 s. Language eng - English Country GB - United Kingdom Keywords molecular property tensors ; normal mode optimatization ; Rayleigh scattering OECD category Physical chemistry R&D Projects GA20-10144S GA ČR - Czech Science Foundation (CSF) GA22-04669S GA ČR - Czech Science Foundation (CSF) EF16_019/0000729 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) Research Infrastructure e-INFRA CZ - 90140 - CESNET, zájmové sdružení právnických osob Method of publishing Limited access Institutional support UOCHB-X - RVO:61388963 UT WOS 000838190200001 EID SCOPUS 85136224133 DOI 10.1039/d2cp02290g Annotation Vibrational frequencies of modes involving intermolecular motions in liquids are relatively small, in the Raman scattering close to the excitation frequency, and the bands may merge into a diverging uninterpretable signal. Raman optical activity (ROA) spectral shapes in this region, however, are structured more and may better reflect the nature of the studied systems. To understand the origin of the signal and its relation to the molecules, ROA spectra of six chiral neat liquids are recorded and analyzed on the basis of molecular dynamics and density functional theory computations. The theory of Raman scattering of liquids is discussed and adapted for modeling based on clusters and periodic boundary conditions. A plain cluster approach is compared to a crystal-like model. The results show that the low-frequency optical activity can be reliably modeled and related to the structure. However, momentary arrangement of molecules leads to large variations of optical activity, and a relatively large number of geometries need to be averaged for accurate simulations. The intermolecular modes are intertwined with intramolecular ones and start to dominate as the frequency goes down. The low-frequency ROA signal thus reflects the chemical composition and coupled with the modeling it provides a welcome means to study the structure and interactions of chiral liquids. Workplace Institute of Organic Chemistry and Biochemistry Contact asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Jana Procházková, Tel.: 220 183 418 Year of Publishing 2023 Electronic address https://doi.org/10.1039/D2CP02290G
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