Abstract
Molecular dynamics simulations in conjunction with a number of network analysis techniques have been carried out to explore the structure of the hydrogen-bond (H-bond) network in mixtures of formamide (FA) and methanol (MeOH) across the entire composition range. Radial distribution functions and pair energy distributions have been utilized for a general insight into the localized interactions. A comprehensive understanding of the structural properties of the H-bond networks including FA…FA, MeOH…MeOH, and FA…MeOH H-bonding interactions has been obtained collectively from the distribution of H-bonds, extended neighborhood analysis, and the geodesic distance distribution. These analyses indicate that formamide molecules prefer formamide molecules not only as immediate hydrogen-bonded neighbors but also as neighbors in their extended neighborhood that spans the neighbors of the immediate neighbors. Methanol molecules are found not to show a strong preference for either of the molecule types. The network analyses utilized in this study reveal that the population and the topological length of chain-like H-bond pathways formed by FA molecules increase with the addition of small amounts of methanol until the mole fractions of each species are equal.
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References
Ball, P.: Water—an enduring mystery. Nature 452, 291–292 (2008)
Stillinger, F.H.: Water revisited. Science 209, 451–457 (1980)
Mishima, O., Stanley, H.E.: The relationship between liquid, supercooled and glassy water. Nature 396, 329–335 (1998)
Blumberg, R.L., Stanley, H.E., Geiger, A., Mausbach, P.: Connectivity of hydrogen bonds in liquid water. J. Chem. Phys. 80, 5230 (1984)
Smith, J.D., Cappa, C.D., Wilson, K.R., Messer, B.M., Cohen, R.C., Saykally, R.J.: Energetics of hydrogen bond network rearrangements in liquid water. Science 306, 851–853 (2004)
Luzar, A., Chandler, D.: Hydrogen-bond kinetics in liquid water. Nature 379, 55–57 (1996)
Ludwig, R.: Water: from clusters to the bulk. Angew. Chem. Int. Ed. 40, 1808–1827 (2001)
Ozkanlar, A., Zhou, T., Clark, A.E.: Towards a unified description of the hydrogen bond network of liquid water: a dynamics based approach. J. Chem. Phys. 141, 214107 (2014)
Bako, I., Megyes, T., Balint, S., Chihaia, V., Bellissent-Funel, M.-C., Krienke, H., Kopf, A., Suh, S.-H.: Hydrogen bonded network properties in liquid formamide. J. Chem. Phys. 132, 014506 (2010)
Bako, I., Bencsura, A., Herrmanson, K., Balint, S., Grosz, T., Chihaia, V., Olah, J.: Hydrogen bond network topology in liquid water and methanol: a graph theory approach. Phys. Chem. Chem. Phys. 15, 15163–15171 (2013)
Cordeiro, J.M.M.: C-H···O and N–H···O hydrogen bonds in liquid amides investigated by Monte Carlo simulation. Int. J. Quant. Chem. 65, 709–717 (1997)
Puhovski, Y.P., Rode, B.M.: Structure and dynamics of liquid formamide. Chem. Phys. 190, 61–82 (1995)
Bako, I., Megyes, T., Balint, S., Grosz, T., Chihaia, V.: Water–methanol mixtures: topology of hydrogen bonded network. Phys. Chem. Chem. Phys. 10, 5004–5011 (2008)
Bako, I., Olah, J., Labas, A., Balint, S., Pusztai, L., Bellissent-Funel, M.-C.: Water–formamide mixtures: topology of the hydrogen-bonded network. J. Mol. Liq. 228, 25–31 (2017)
Ozkanlar, A.: Structural properties of hydrogen-bond network in liquid formamide–water mixtures. Fluid Phase Equilib. 456, 98–108 (2018)
Vaisman, I.I., Berkowitz, M.L.: Local structural order and molecular associations in water–DMSO mixtures. Molecular dynamics study. J. Am. Chem. Soc. 114, 7889–7896 (1992)
Bellissent-Funel, M.-C., Nasr, S., Bosio, L.: X-ray and neutron scattering studies of the temperature and pressure dependence of the structure of liquid formamide. J. Chem. Phys. 106, 7913 (1997)
Tsuchida, E.: Ab initio molecular-dynamics study of liquid formamide. J. Chem. Phys. 121, 4740 (2004)
Jadzyn, J., Swiergiel, J.: On similarity of hydrogen-bonded networks in liquid formamide and water as revealed in the static dielectric studies. Phys. Chem. Chem. Phys. 14, 3170–3175 (2012)
Takamuku, T., Yamaguchia, T., Asato, M., Matsumoto, M., Nishi, N.: Structure of clusters in methanol–water binary solutions studied by mass spectrometry and X-ray diffraction. Z Naturforsch. 55a, 513–525 (2000)
Andanson, J.M., Bopp, P., Soetens, J.C.: Relation between hydrogen bonding and intramolecular motions in liquid and supercritical methanol. J. Mol. Liq. 129, 101–107 (2006)
Voet, D., Voet, J.G.: Biochemistry. Wiley, Hoboken (2011)
Kannan, P.P., Karthick, N.K., Arivazhagan, G.: Hydrogen bond interactions in the binary solutions of formamide with methanol: FTIR spectroscopic and theoretical studies. Spectrochim. Acta A 229, 117892 (2020)
Abdelmoulahi, H., Trabelsi, S., Nasr, S., Bellissent-Funel, M.-C.: Hydrogen-bond network in liquid formamide methanol mixture as studied by neutron scattering and density functional theory. J. Mol. Liq. 271, 8–15 (2018)
Stangret, J., Kamienska-Piotrowicz, E., Laskowska, K.: FT-IR studies of molecular interactions in formamide–methanol mixtures. Vib. Spectrosc. 44, 324–330 (2007)
Lovas, F.J., Suenram, R.D., Fraser, G.T., Gillies, C.W., Zozom, J.: The microwave spectrum of formamide–water and formamide–methanol complexes. J. Chem. Phys. 88, 722 (1988)
Fu, A., Du, D., Zhou, Z.: Density functional theory study of the hydrogen bonding interaction of 1:1 complexes of formamide with methanol. Chem. Phys. Lett. 377, 537–543 (2003)
Fu, A., Du, D., Zhou, Z.: Study of the formamide–methanol dimer with ab initio and density functional theory methods. Int. J. Quantum Chem. 97, 865–875 (2004)
Jasien, P.G., Stevens, W.J.: Ab initio study of the hydrogen bonding interactions of formamide with water and methanol. J. Chem. Phys. 84, 3271 (1986)
Sathyan, N., Santhanam, V., Sobhanadri, J.: Ab initio calculations on some binary systems involving hydrogen bonds. J. Mol. Struct. (Theochem) 333, 179–189 (1995)
Chen, B., Potoff, J.J., Siepmann, J.I.: Monte Carlo calculations for alcohols and their mixtures with alkanes. Transferable potentials for phase equilibria. 5. United-atom description of primary, secondary, and tertiary alcohols. J. Phys. Chem. B 105, 3093–3104 (2001)
Vanommeslaeghe, K., Hatcher, E., Acharya, C., Kundu, S., Zhong, S., Shim, J., Darian, E., Guvench, O., Lopes, P., Vorobyov, I., Mackerell, A.D., Jr.: CHARMM general force field: a force field for drug-like molecules compatible with the CHARMM all-atom additive biological force fields. J. Comput. Chem. 31, 671–690 (2010)
Martins, F., Leitao, R.E., Nunes, N.: Volumetric and refractive index study of the ternary mixture methanol/formamide/acetonitrile at 298.15 K. J. Mol. Liq. 234, 463–468 (2017)
Todorov, I.T., Smith, W., Trachenko, K., Dove, M.T.: DL_POLY_3: new dimensions in molecular dynamics simulations via massive parallelism. J. Mater. Chem. 16, 1911–1918 (2006)
Yamaguchi, T., Hidaka, K., Soper, A.K.: The structure of liquid methanol revisited: a neutron diffraction experiment at −80 °C and +25 °C. Mol. Phys. 96, 1159–1168 (1999)
Yamaguchi, T., Hidaka, K., Soper, A.K.: Erratum The structure of liquid methanol revisited: a neutron diffraction experiment at − 80 °C and + 25 °C. Mol. Phys. 97, 603–605 (1999)
Ohtaki, H., Funaki, A., Rode, B.M., Reibnegger, G.J.: The structure of liquid formamide studied by means of X-ray diffraction and ab ınitio LCGO-MO-SCF calculations. Bull. Chem. Soc. Jpn. 56, 2116–2121 (1983)
Ozkanlar, A., Clark, A.E.: ChemNetworks: a complex network analysis tool for chemical systems. J. Comput. Chem. 35, 495–505 (2014)
Floyd, R.W.: Algorithm 97 shortest path. Commun. ACM 5, 345 (1962)
Warshall, S.: A theorem on boolean matrices. J. ACM 9, 11–12 (1962)
Ozkanlar, A., Kelley, M.P., Clark, A.E.: Water organization and dynamics on mineral surfaces ınterrogated by graph theoretical analyses of ıntermolecular chemical networks. Minerals 4, 118–129 (2014)
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The author gratefully acknowledges the computing time provided by Erciyes University Computer Center.
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Ozkanlar, A. Structure of the Hydrogen-Bond Network in Binary Mixtures of Formamide and Methanol. J Solution Chem 50, 257–276 (2021). https://doi.org/10.1007/s10953-021-01058-7
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DOI: https://doi.org/10.1007/s10953-021-01058-7