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Open AccessArticle
Density Functional Theory Calculations for Interpretation of Infra-Red Spectra of Liquid Crystalline Chiral Compound
by
Aleksandra Deptuch
Aleksandra Deptuch 1,*
,
Natalia Górska
Natalia Górska 2,
Michaela Murzyniec
Michaela Murzyniec 2,
Monika Srebro-Hooper
Monika Srebro-Hooper 2
,
James Hooper
James Hooper 2,
Magdalena Dziurka
Magdalena Dziurka 2 and
Magdalena Urbańska
Magdalena Urbańska 3
1
Institute of Nuclear Physics Polish Academy of Sciences, Radzikowskiego 152, PL-31342 Kraków, Poland
2
Faculty of Chemistry, Jagiellonian University, Gronostajowa 2, PL-30387 Kraków, Poland
3
Institute of Chemistry, Military University of Technology, Kaliskiego 2, PL-00908 Warsaw, Poland
*
Author to whom correspondence should be addressed.
Crystals 2024, 14(7), 645; https://doi.org/10.3390/cryst14070645 (registering DOI)
Submission received: 24 June 2024
/
Revised: 10 July 2024
/
Accepted: 11 July 2024
/
Published: 13 July 2024
Abstract
The experimental IR spectra of (S)-4′-(1-methylheptyloxycarbonyl) biphenyl-4-yl 4-[2-(2,2,3,3,4,4,4-heptafluorobutoxy) ethyl-1-oxy]-2-fluorobenzoate in the crystal phase are analyzed with the help of dispersion-corrected density functional theory (DFT+D3) calculations for isolated molecular monomer and dimer models, and a periodic model computed at the extended density functional tight-binding (xTB) level of theory. It is found that the frequency scaling coefficients obtained with the results of the molecular calculations are good matches for the crystal phase, being close to 1. The molecular and periodic models both confirm that varied intra- and intermolecular interactions are crucial in order to reproduce the broadened shape of the experimental band related to C=O stretching; the key factors are the conjugation of the ester groups with the aromatic rings and the varied intermolecular chemical environments, wherein the C=O group that bridges the biphenyl and F-substituted phenyl groups seems particularly sensitive. The C=O stretching vibrations are investigated as a function of temperature, covering the range of the crystal, smectic CA*, smectic C* and isotropic liquid phases. The structure changes are followed based on the X-ray diffraction patterns collected in the same temperatures as the IR spectra. The experimental and computational results taken together indicate that the amount of weak C=O…H-C hydrogen bonds between the molecules in the smectic layers decreases with increasing temperature.
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MDPI and ACS Style
Deptuch, A.; Górska, N.; Murzyniec, M.; Srebro-Hooper, M.; Hooper, J.; Dziurka, M.; Urbańska, M.
Density Functional Theory Calculations for Interpretation of Infra-Red Spectra of Liquid Crystalline Chiral Compound. Crystals 2024, 14, 645.
https://doi.org/10.3390/cryst14070645
AMA Style
Deptuch A, Górska N, Murzyniec M, Srebro-Hooper M, Hooper J, Dziurka M, Urbańska M.
Density Functional Theory Calculations for Interpretation of Infra-Red Spectra of Liquid Crystalline Chiral Compound. Crystals. 2024; 14(7):645.
https://doi.org/10.3390/cryst14070645
Chicago/Turabian Style
Deptuch, Aleksandra, Natalia Górska, Michaela Murzyniec, Monika Srebro-Hooper, James Hooper, Magdalena Dziurka, and Magdalena Urbańska.
2024. "Density Functional Theory Calculations for Interpretation of Infra-Red Spectra of Liquid Crystalline Chiral Compound" Crystals 14, no. 7: 645.
https://doi.org/10.3390/cryst14070645
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