Molecular Isomerization in n-Propanol Dimers

  • I. Doroshenko Taras Shevchenko National University of Kyiv
  • Ye. Vaskivskyi Taras Shevchenko National University of Kyiv, Jozef Stefan Institute
  • Ye. Chernolevska Taras Shevchenko National University of Kyiv, Jozef Stefan Institute
  • L. Meyliev Karshi State University
  • B. Kuyliev Karshi State University
Keywords: molecular isomerization, dimer, n-propanol, hydrogen bonding, quantum chemistry


The molecular isomerization has been studied in n-propanol dimers by quantum-chemical calculations with the DFT method. 25 combinations of molecular pairs are calculated with and without consideration of the dielectric constant of n-propanol. Such approach allowed us to determine the most stable configurations of alcohol dimers. It has been shown that dimers of n-propanol are mostly (77.1%) formed by only 5 of 25 possible configurations at room temperature and by 2 combinations (87.3%) at the melting point. The size distribution of dimers and the spectral dispersion in the region of free and bonded O–H stretching vibrations are calculated.


A. Vrhovsek, O. Gereben, A. Jamnik, L. Pusztai. Hydrogen bonding and molecular aggregates in liquid methanol, ethanol, and 1-propanol. J. Phys. Chem. B 115 (46), 13473 (2011).

Y. Chernolevska, Y. Vaskivskyi, I. Doroshenko. Cluster Structure of Monohydroxyl Alcohols in Condensed State (LAMBERT Acad. Publ., 2016) ISBN: 978-3-659-86995-2 (in Russian).

V. Pogorelov, Y. Chernolevska, Y. Vaskivskyi, L.G.M. Pettersson, I. Doroshenko, V. Sablinskas, V. Balevicius, J. Ceponkus, K. Kovaleva, A. Malevich, et al. Structural transformations in bulk and matrix-isolated methanol from measured and computed infrared spectroscopy. J. Mol. Liq. 216, 53 (2016).

I. Doroshenko, G. Pitsevich, V. Sablinskas. Cluster Structure of Liquid Alcohols: Vibrational Spectroscopy Study (LAMBERT Acad. Publ., 2012) [ISBN: 978-3-8484-2251-7] (in Russian).

Y.A. Chernolevska, I.Y. Doroshenko, V.E. Pogorelov, Y.V. Vaskivskyi, V. Sablinskas, V. Balevicius, A. Isaev. Theoretical and experimental researches of methanol clusters in low-temperature matrices. Ukr. J. Phys. 60 (11), 1089 (2015).

I. Doroshenko, V. Balevicius, G. Pitsevich, K. Aidas, V. Sablinskas, V.Pogorelov. FTIR/PCA study of propanol in argon matrix: The initial stage of clustering and conformational transitions. Low Temp. Phys. 40 (12), 1077 (2014).

M.I. Sulaiman, S. Yang, A.M. Ellis. Infrared spectroscopy of methanol and methanol/water clusters in helium nanodroplets: The OH stretching region. J. Phys. Chem. A 121 (4), 771 (2017).

M. Goulart, P. Bartl, A. Mauracher, F. Zappa, A.M. Ellis, P. Scheier. Electron-driven ionization of large methanol clusters in helium nanodroplets. Phys. Chem. Chem. Phys. 15 (10), 3577 (2013).

K. Bloch, C.P. Lawrence. Hydrogen bond lifetimes and clustering of methanol in carbon tetrachloride solutions. J. Phys. Chem. B 114 (1), 293 (2010).

T. Kobayashi, R. Shishido, K. Mizuse, A. Fujii, J.-L. Kuo. Structures of hydrogen bond networks formed by a few tens of methanol molecules in the gas phase: size-selective infrared spectroscopy of neutral and protonated methanol clusters. Phys. Chem. Chem. Phys. 15 (24), 9523 (2013).

I.Y. 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. 37 (7), 604 (2011).

Y. Chernolevska, V. Pogorelov, Y. Vaskivskyi, I. Doroshenko. Temperature-induced evolution of a cluster structure in N-nonan-1-Ol: Experimental study and quantum-chemistry calculations. Ukr. J. Phys. 61 (6), 478 (2016).

G.A. Pitsevich, I.Y. Doroshenko, V.Y. Pogorelov, V. Sablinskas, V. Balevicius. Structure and vibrational spectra of gauche- and trans-conformers of ethanol: Nonempirical anharmonic calculations and FTIR spectra in argon matrices. Low Temp. Phys. 39 (4), 389 (2013).

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).

D. Loru, I. Pe˜na, M.E. Sanz. Ethanol dimer: Observation of three new conformers by broadband rotational spectroscopy. J. Mol. Spectrosc. 335, 93 (2017).

Y. Yu, Y. Wang, N. Hu, K. Lin, X. Zhou, S. Liu. CB - H stretching vibrations as a new probe for conformation of n-propanol in gaseous and liquid states. Phys. Chem. Chem. Phys. 18 (15), 10563 (2016).

T.N. Wassermann, M.A. Suhm, P. Roubin, S. Coussan. Isomerization around C-C and C-O bonds in 1-propanol: Collisional relaxation in supersonic jets and selective IR photo-isomerization in cryogenic matrices. J. Mol. Struct. 1025, 20 (2012).

G.А. Pitsevich, I.Y. Doroshenko, V.E. Pogorelov, V. Shablinskas, V. Balevichus, Е.N. Kozlovskaya. Nonempiric anharmonic computations of ir spectra of ethanol conformers in b3lyp/сс-pvqz approximation (stretch С-Н vibrations). Am. J. Chem. 2 (4), 218 (2012).

D. Katsikadakos, Y. Hardalupas, A.M.K.P. Taylor, P.A. Hunt. Hydrogen abstraction from n-butanol by the methyl radical: High level ab initio study of abstraction pathways and the importance of low energy rotational conformers. Phys. Chem. Chem. Phys. 14, 9615 (2012).

J. Moc, J.M. Simmie, H.J. Curran. The elimination of water from a conformationally complex alcohol: A computational study of the gas phase dehydration of n-butanol. J. Mol. Struct. 928, 149 (2009).

T.N. Wassermann, P. Zielke, J.J. Lee, C. C'ezard, M.A. Suhm. Structural preferences, argon nanocoating, and dimerization of n-alkanols as revealed by oh stretching spectroscopy in supersonic jet. J. Phys. Chem. A 111 (31), 7437 (2007).

V.G. Baonza, M. Taravillo, A. Cazorla, S. Casado, M. C'aceres. N-pentanol at high pressures: Rotational isomerism in the liquid phase and the liquid-solid phase transition. J. Chem. Phys. 124 (4), 44508 (2006).

M.A. Czarnecki, D. Wojtk'ow, K. Haufa. Rotational isomerism of butanols: infrared, near-infrared and DFT study. Chem. Phys. Lett. 431, 294 (2006).

K. Kahn, T.C. Bruice. Focal-point conformational analysis of ethanol, propanol, and isopropanol. Chem. Phys. Chem. 6, 487 (2005).

K.B. Be'c, Y. Futami, M.J. W'ojcik, Y. Ozaki. A spectroscopic and theoretical study in the near-infrared region of low concentration aliphatic alcohols. Phys. Chem. Chem. Phys. 18 (19), 13666 (2016).

M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, et al. Gaussian 09. Revision D.01, (Gaussian, 2013).

M.D. Hanwell, D.E. Curtis, D.C. Lonie, T. Vandermeersch, E. Zurek, G.R. Hutchison. Avogadro: An advanced semantic chemical editor, visualization, and analysis platform. J. Cheminform. 4 (1), 17 (2012).

R. Dennington, T.A. Keith, J.M. Millam. GaussView, Version 5, (Semichem, 2009).

Ye. Vaskivskyi, Ye. Chernolevska, A. Vasylieva, V. Pogorelov, R. Platakyte, J. Stocka, I. Doroshenko. 1-Hexanol conformers in a nitrogen matrix: FTIR study and high-level ab initio calculations. J. Mol. Liq. 278, 362 (2019).

CRC Handbook of Chemistry and Physics, edited by W.M. Haynes (CRC press, 2012).

How to Cite
Doroshenko, I., Vaskivskyi, Y., Chernolevska, Y., Meyliev, L., & Kuyliev, B. (2020). Molecular Isomerization in n-Propanol Dimers. Ukrainian Journal of Physics, 65(4), 291.
Optics, atoms and molecules

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