Influence of the Environment on Structure and Vibrational Spectra of Methanol Clusters
DOI:
https://doi.org/10.15407/ujpe71.1.39Keywords:
methanol, hydrogen bonding, IR spectra, cluster, argonAbstract
The study investigates the influence of the environment on the geometric parameters and IR absorption spectra of small methanol clusters (monomer, dimer, and trimer) using quantum chemical calculations with the DFT method (B3LYP/cc-pVTZ). It is shown that argon atoms affect the structure of the methanol molecule more strongly than methanol molecules do. The main effect of the environment on the structure of methanol molecules consists in the elongation of the C–H and O–H bonds, which manifests itself in the IR spectra as a red shift of the corresponding absorption bands. A comparison of the modeling results for methanol clusters of different sizes demonstrated that the magnitude of the spectral shift decreases with an increasing number of molecules in the cluster. The comparison of the modeling results with experimental data led to the conclusion that this approach is suitable for interpreting the spectra of monohydric alcohols in matrix isolation.
References
1. V. Pogorelov, L. Bulavin, I. Doroshenko, O. Fesjun, O. Veretennikov. The structure of liquid alcohols and the temperature dependence of vibrational bandwidth. J. Mol. Struct. 708 (1-3), 61 (2004).
https://doi.org/10.1016/j.molstruc.2004.03.003
2. P. Golub, I. Doroshenko, V. Pogorelov. Quantum-chemical modeling of energy parameters and vibrational spectra of chain and cyclic clusters of monohydric alcohols. Phys. Lett. A 378, 1937 (2014).
https://doi.org/10.1016/j.physleta.2014.04.032
3. V. Pogorelov, Ye. Chernolevska, Ye. Vaskivskyi, L.G.M. Pettersson, I. Doroshenko, V. Sablinskas, V. Balevicius, Ju. Ceponkus, K. Kovaleva, A. Malevich, G. Pitsevich. Structural transformations in bulk and matrix-isolated methanol from measured and computed infrared spectroscopy. J. Mol. Liq. 216, 53 (2016).
https://doi.org/10.1016/j.molliq.2015.12.099
4. O. Mishchuk, I. Doroshenko, V.Sablinskas, V.Balevicius. Temperature evolution of cluster structure in n-hexanol, isolated in Ar and N2 matrices and in condensed states. Struct. Chem. 27, 243 (2016).
https://doi.org/10.1007/s11224-015-0692-7
5. V. Pogorelov, A. Yevglevsky, I. Doroshenko, L. Berezovchuk, Yu. Zhovtobryuch. Nanoscale molecular clusters and vibrational relaxation in simple alcohols. Superlattices and microstructures 44 (4-5), 571 (2006).
https://doi.org/10.1016/j.spmi.2008.01.014
6. Z. Mielke, S. Coussan, K. Mierzwicki, P. Roubin, M. Sa ldyka. The complexes between CH3OH and CF4. Infrared matrix isolation and theoretical studies. J. Phys. Chem. A. 110, 4712 (2006).
https://doi.org/10.1021/jp057300t
7. M. Van Thiel, E.D. Becker, G.C. Pimentel. Infrared studies of hydrogen bonding of methanol by the matrix isolation technique. J. Chem. Phys. 27, 95 (1957).
https://doi.org/10.1063/1.1743725
8. I. Doroshenko, V. Pogorelov, V. Sablinskas, V. Balevicius. Matrix-isolation study of cluster formation in methanol: O-H stretching region. J. Mol. Liq. 157, 142 (2010).
https://doi.org/10.1016/j.molliq.2010.09.003
9. I.Yu. Doroshenko. Matrix isolation study of the formation of methanol cluster structures in the spectral region of C-O and O-H stretch vibrations. Low.Temp.Phys. 57 (7), 604 (2011).
https://doi.org/10.1063/1.3643482
10. A. Vasylieva, I. Doroshenko, O. Doroshenko, V. Pogorelov. Effect of argon environment on small water clusters in matrix isolation. Low.Temp.Phys. 45(6), 736 (2019).
https://doi.org/10.1063/1.5103255
11. I. Doroshenko, M. Onuk, L. Meyliev, B. Kuyliev. Conformational composition of propanol in gaseous state and in matrix isolation. Mol. Cryst. Liq. Cryst. 747(1), 81 (2022).
https://doi.org/10.1080/15421406.2022.2066795
12. I. Doroshenko, M. Onuk, A. Nekboev, B. Kuyliev. Influence of an argon matrix on trapped ethanol clusters. Low Temp. Phys. 51, 480 (2025).
https://doi.org/10.1063/10.0036207
13. S.G. Stepanian, L. Adamowicz. Influence of matrices on the low-temperature IR spectra of the formic acid molecule isolated in inert gas crystals. Low Temp. Phys. 46, 192 (2020).
https://doi.org/10.1063/10.0000534
14. S.G. Stepanian, A.Yu. Ivanov, L. Adamowicz. Effect of lowtemperature argon matrices on the IR spectra and structure of flexible N-acetylglycine molecules. Low Temp. Phys. 42, 1167 (2016).
https://doi.org/10.1063/1.4973702
15. M.J. Frisch, G.W. Trucks, H.B. Schlegel et al. Gaussian 09 Rev. D.1. (Gaussian Inc, Wallingford 2009).
16. I. Doroshenko, V. Pogorelov, V. Sablinskas. Infrared absorption spectra of monohydric alcohols. Dataset Papers in Chemistry. 2013, 329406 (2013).
https://doi.org/10.7167/2013/329406
17. V. Pogorelov, I. Doroshenko, P. Uvdal, V. Balevicius, V. Sablinskas. Temperature-controlled kinetics of the growth and relaxation of alcohol clusters in an argon matrix. Mol. Phys. 108, 2165 (2010).
Downloads
Published
How to Cite
Issue
Section
License
Copyright Agreement
License to Publish the Paper
Kyiv, Ukraine
The corresponding author and the co-authors (hereon referred to as the Author(s)) of the paper being submitted to the Ukrainian Journal of Physics (hereon referred to as the Paper) from one side and the Bogolyubov Institute for Theoretical Physics, National Academy of Sciences of Ukraine, represented by its Director (hereon referred to as the Publisher) from the other side have come to the following Agreement:
1. Subject of the Agreement.
The Author(s) grant(s) the Publisher the free non-exclusive right to use the Paper (of scientific, technical, or any other content) according to the terms and conditions defined by this Agreement.
2. The ways of using the Paper.
2.1. The Author(s) grant(s) the Publisher the right to use the Paper as follows.
2.1.1. To publish the Paper in the Ukrainian Journal of Physics (hereon referred to as the Journal) in original language and translated into English (the copy of the Paper approved by the Author(s) and the Publisher and accepted for publication is a constitutive part of this License Agreement).
2.1.2. To edit, adapt, and correct the Paper by approval of the Author(s).
2.1.3. To translate the Paper in the case when the Paper is written in a language different from that adopted in the Journal.
2.2. If the Author(s) has(ve) an intent to use the Paper in any other way, e.g., to publish the translated version of the Paper (except for the case defined by Section 2.1.3 of this Agreement), to post the full Paper or any its part on the web, to publish the Paper in any other editions, to include the Paper or any its part in other collections, anthologies, encyclopaedias, etc., the Author(s) should get a written permission from the Publisher.
3. License territory.
The Author(s) grant(s) the Publisher the right to use the Paper as regulated by sections 2.1.1–2.1.3 of this Agreement on the territory of Ukraine and to distribute the Paper as indispensable part of the Journal on the territory of Ukraine and other countries by means of subscription, sales, and free transfer to a third party.
4. Duration.
4.1. This Agreement is valid starting from the date of signature and acts for the entire period of the existence of the Journal.
5. Loyalty.
5.1. The Author(s) warrant(s) the Publisher that:
– he/she is the true author (co-author) of the Paper;
– copyright on the Paper was not transferred to any other party;
– the Paper has never been published before and will not be published in any other media before it is published by the Publisher (see also section 2.2);
– the Author(s) do(es) not violate any intellectual property right of other parties. If the Paper includes some materials of other parties, except for citations whose length is regulated by the scientific, informational, or critical character of the Paper, the use of such materials is in compliance with the regulations of the international law and the law of Ukraine.
6. Requisites and signatures of the Parties.
Publisher: Bogolyubov Institute for Theoretical Physics, National Academy of Sciences of Ukraine.
Address: Ukraine, Kyiv, Metrolohichna Str. 14-b.
Author: Electronic signature on behalf and with endorsement of all co-authors.
.png){kind=small}
