Structures of glass-forming liquids by x-ray scattering: Glycerol, xylitol, and D-sorbitol

Chen, Zhenxuan; Huang, Chengbin; Yao, Xin; Benmore, Chris J.; Yu, Lian

doi:10.1063/5.0073986

Title: Structures of glass-forming liquids by x-ray scattering: Glycerol, xylitol, and D-sorbitol

Journal Article · 29 December 2021 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/5.0073986 · OSTI ID:1846389

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Univ. of Wisconsin, Madison, WI (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

In this work, synchrotron X-ray scattering has been used to investigate three liquid polyalcohols of different sizes (glycerol, xylitol and D-sorbitol) from above the glass transition temperatures $$T_g$$ to below. We focus on two structural orders: the association of the polar OH groups by hydrogen bonds (HBs) and the packing of the non-polar hydrocarbon groups. We find that the two structural orders evolve very differently reflecting the different natures of bonding. Upon cooling from 400 K, the O$$\cdots$$O correlation at 2.8 Å increases significantly in all three systems, indicating more HBs, until kinetic arrest at $$T_g$$; the increase is well described by an equilibrium between bonded and non-bonded OH with ΔH = 9.1 kJ/mol and ΔS = 13.4 J/mol/K. When heated above $$T_g$$, glycerol loses the fewest HBs per OH, followed by xylitol and by D-sorbitol, in the same order the number of OH groups per molecule increases (3, 5, and 6). The pair correlation functions of all three liquids show exponentially damped density modulations of wavelength 4.5 Å, which are associated with the main scattering peak and with the intermolecular C$$\cdots$$C correlation. In this respect, glycerol is the most ordered with the most persistent density ripples, followed by D-sorbitol and by xylitol. Heating above $$T_g$$ causes faster damping of the density ripples with the rate of change being the slowest in xylitol, followed by glycerol and by D-sorbitol. Given the different dynamic fragility of the three liquids (glycerol being the strongest and D-sorbitol the most fragile), we relate our results to the current theories of the structural origin for the difference. We find that the fragility difference is better understood on the basis of the thermal stability of HB clusters than that of the structure associated with the main scattering peak.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1846389

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 24 Vol. 155; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

References (57)

A neutron diffraction study of the structure of evaporated amorphous germanium Etherington, G.; Wright, A. C.; Wenzel, J. T. Journal of Non-Crystalline Solids, Vol. 48, Issue 2-3 https://doi.org/10.1016/0022-3093(82)90165-x	journal	April 1982
Medium-range structure in glasses and low-Q structure in neutron and X-ray scattering data Gaskell, Philip H. Journal of Non-Crystalline Solids, Vol. 351, Issue 12-13 https://doi.org/10.1016/j.jnoncrysol.2005.01.011	journal	May 2005
Strong geometric frustration in model glassformers Royall, C. Patrick; Malins, Alex; Dunleavy, Andrew J. Journal of Non-Crystalline Solids, Vol. 407 https://doi.org/10.1016/j.jnoncrysol.2014.08.017	journal	January 2015
Structure and dynamics of monohydroxy alcohols—Milestones towards their microscopic understanding, 100 years after Debye Böhmer, Roland; Gainaru, Catalin; Richert, Ranko Physics Reports, Vol. 545, Issue 4 https://doi.org/10.1016/j.physrep.2014.07.005	journal	December 2014
On the X-ray Scattering Pre-peak of Linear Mono-ols and the Related Microstructure from Computer Simulations Požar, Martina; Bolle, Jennifer; Sternemann, Christian The Journal of Physical Chemistry B, Vol. 124, Issue 38 https://doi.org/10.1021/acs.jpcb.0c05932	journal	August 2020
Hydrogen Bonding Slows Down Surface Diffusion of Molecular Glasses Chen, Yinshan; Zhang, Wei; Yu, Lian The Journal of Physical Chemistry B, Vol. 120, Issue 32 https://doi.org/10.1021/acs.jpcb.6b05658	journal	August 2016
Optimized intermolecular potential functions for liquid alcohols Jorgensen, William L. The Journal of Physical Chemistry, Vol. 90, Issue 7 https://doi.org/10.1021/j100398a015	journal	March 1986
Computational Analysis of the Potential Energy Surfaces of Glycerol in the Gas and Aqueous Phases: Effects of Level of Theory, Basis Set, and Solvation on Strongly Intramolecularly Hydrogen-Bonded Systems Callam, Christopher S.; Singer, Sherwin J.; Lowary, Todd L. Journal of the American Chemical Society, Vol. 123, Issue 47 https://doi.org/10.1021/ja011785r	journal	November 2001
Structure of Methanol Confined in MCM-41 Investigated by Large-Angle X-ray Scattering Technique Takamuku, Toshiyuki; Maruyama, Hirokazu; Kittaka, Shigeharu The Journal of Physical Chemistry B, Vol. 109, Issue 2 https://doi.org/10.1021/jp047359k	journal	January 2005
Effects of Temperature on the Properties of Glycerol: A Computer Simulation Study of Five Different Force Fields Jahn, David A.; Akinkunmi, Frederick O.; Giovambattista, Nicolas The Journal of Physical Chemistry B, Vol. 118, Issue 38 https://doi.org/10.1021/jp5059098	journal	September 2014
A structural signature of liquid fragility Mauro, N. A.; Blodgett, M.; Johnson, M. L. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5616	journal	August 2014
Thermodynamic signature of growing amorphous order in glass-forming liquids Biroli, G.; Bouchaud, J. -P.; Cavagna, A. Nature Physics, Vol. 4, Issue 10 https://doi.org/10.1038/nphys1050	journal	August 2008
Glycerol condensed phases Part II.A molecular dynamics study of the conformational structure and hydrogen bonding Chelli, Riccardo; Procacci, Piero; Cardini, Gianni Physical Chemistry Chemical Physics, Vol. 1, Issue 5 https://doi.org/10.1039/a808957d	journal	January 1999
Glycerol condensed phases Part I. A molecular dynamics study Chelli, Riccardo; Procacci, Piero; Cardini, Gianni Physical Chemistry Chemical Physics, Vol. 1, Issue 5 https://doi.org/10.1039/a808958b	journal	January 1999
The structure of glycerol in the liquid state: a neutron diffraction study Towey, J. J.; Soper, A. K.; Dougan, L. Physical Chemistry Chemical Physics, Vol. 13, Issue 20 https://doi.org/10.1039/c0cp02136a	journal	January 2011
Identifying and characterising the different structural length scales in liquids and glasses: an experimental approach Salmon, Philip S.; Zeidler, Anita Physical Chemistry Chemical Physics, Vol. 15, Issue 37 https://doi.org/10.1039/c3cp51741a	journal	January 2013
X-ray scattering study and molecular simulation of glass forming liquids: Propylene carbonate and salol Eckstein, E.; Qian, J.; Hentschke, R. The Journal of Chemical Physics, Vol. 113, Issue 11 https://doi.org/10.1063/1.1288907	journal	September 2000
Decay of Pair Correlations in Hard Sphere Fluids Perry, P.; Throop, G. J. The Journal of Chemical Physics, Vol. 57, Issue 5 https://doi.org/10.1063/1.1678497	journal	September 1972
Microstructure of neat alcohols: A molecular dynamics study Zoranić, Larisa; Sokolić, Franjo; Perera, Aurélien The Journal of Chemical Physics, Vol. 127, Issue 2 https://doi.org/10.1063/1.2753482	journal	July 2007
Hydrogen bonding in liquid methanol and ethanol determined by x‐ray diffraction Narten, A. H.; Habenschuss, A. The Journal of Chemical Physics, Vol. 80, Issue 7 https://doi.org/10.1063/1.447093	journal	April 1984
Temperature dependence of the low‐ and high‐frequency Raman scattering from liquid water Walrafen, G. E.; Fisher, M. R.; Hokmabadi, M. S. The Journal of Chemical Physics, Vol. 85, Issue 12 https://doi.org/10.1063/1.451384	journal	December 1986
Short‐range order in glycerol. A molecular dynamics study Root, Leslie J.; Stillinger, Frank H. The Journal of Chemical Physics, Vol. 90, Issue 2 https://doi.org/10.1063/1.456176	journal	January 1989
Asymptotic decay of correlations in liquids and their mixtures Evans, R.; Leote de Carvalho, R. J. F.; Henderson, J. R. The Journal of Chemical Physics, Vol. 100, Issue 1 https://doi.org/10.1063/1.466920	journal	January 1994
Structural studies of an organic liquid through the glass transition Leheny, Robert L.; Menon, Narayanan; Nagel, Sidney R. The Journal of Chemical Physics, Vol. 105, Issue 17 https://doi.org/10.1063/1.472561	journal	November 1996
Effect of pressure on hydrogen bonding in glycerol: A molecular dynamics investigation Root, Leslie J.; Berne, B. J. The Journal of Chemical Physics, Vol. 107, Issue 11 https://doi.org/10.1063/1.474776	journal	September 1997
Benchmark oxygen-oxygen pair-distribution function of ambient water from x-ray diffraction measurements with a wide Q -range Skinner, Lawrie B.; Huang, Congcong; Schlesinger, Daniel The Journal of Chemical Physics, Vol. 138, Issue 7 https://doi.org/10.1063/1.4790861	journal	February 2013
Liquid 1-propanol studied by neutron scattering, near-infrared, and dielectric spectroscopy Sillrén, P.; Matic, A.; Karlsson, M. The Journal of Chemical Physics, Vol. 140, Issue 12 https://doi.org/10.1063/1.4868556	journal	March 2014
The structure of water around the compressibility minimum Skinner, L. B.; Benmore, C. J.; Neuefeind, J. C. The Journal of Chemical Physics, Vol. 141, Issue 21 https://doi.org/10.1063/1.4902412	journal	December 2014
Direct observation in 3d of structural crossover in binary hard sphere mixtures Statt, Antonia; Pinchaipat, Rattachai; Turci, Francesco The Journal of Chemical Physics, Vol. 144, Issue 14 https://doi.org/10.1063/1.4945808	journal	April 2016
Revealing the three-dimensional structure of liquids using four-point correlation functions Zhang, Zhen; Kob, Walter Proceedings of the National Academy of Sciences, Vol. 117, Issue 25 https://doi.org/10.1073/pnas.2005638117	journal	June 2020
Structural studies of liquid D-glycerol by neutron diffraction Champeney, D. C.; Joarder, R. N.; Dore, J. C. Molecular Physics, Vol. 58, Issue 2 https://doi.org/10.1080/00268978600101201	journal	June 1986
Technical Report: Automatic Experiments at the European Synchrotron Radiation Facility MX Beam-lines Leonard, Gordon; McCarthy, Joanne; Nurizzo, Didier Synchrotron Radiation News, Vol. 20, Issue 3 https://doi.org/10.1080/08940880701401136	journal	May 2007
Two-dimensional detector software: From real detector to idealised image or two-theta scan Hammersley, A. P.; Svensson, S. O.; Hanfland, M. High Pressure Research, Vol. 14, Issue 4-6, p. 235-248 https://doi.org/10.1080/08957959608201408	journal	January 1996
The density of random close packing of spheres Scott, G. D.; Kilgour, D. M. Journal of Physics D: Applied Physics, Vol. 2, Issue 6 https://doi.org/10.1088/0022-3727/2/6/311	journal	June 1969
A practical method for the deconvolution of experimental curves Jones, A. F.; Misell, D. L. British Journal of Applied Physics, Vol. 18, Issue 10 https://doi.org/10.1088/0508-3443/18/10/315	journal	October 1967
Integral equation theory of thermodynamics, pair structure, and growing static length scale in metastable hard sphere and Weeks-Chandler-Andersen fluids Zhou, Yuxing; Mei, Baicheng; Schweizer, Kenneth S. Physical Review E, Vol. 101, Issue 4 https://doi.org/10.1103/PhysRevE.101.042121	journal	April 2020
Origin of liquid fragility Ryu, Chae Woo; Egami, Takeshi Physical Review E, Vol. 102, Issue 4 https://doi.org/10.1103/PhysRevE.102.042615	journal	October 2020
Role of hydrogen bonds and molecular structure in relaxation dynamics of pentiol isomers Pawlus, S.; Grzybowski, A.; Paluch, M. Physical Review E, Vol. 85, Issue 5 https://doi.org/10.1103/PhysRevE.85.052501	journal	May 2012
Correlation between temperature variations of static and dynamic properties in glass-forming liquids Voylov, D. N.; Griffin, P. J.; Mercado, B. Physical Review E, Vol. 94, Issue 6 https://doi.org/10.1103/PhysRevE.94.060603	journal	December 2016
Structure and Resistivity of Liquid Metals Ashcroft, N. W.; Lekner, J. Physical Review, Vol. 145, Issue 1 https://doi.org/10.1103/physrev.145.83	journal	May 1966
X-Ray Diffraction in Liquids: Primary Normal Alcohols Stewart, G. W.; Morrow, Roger M. Physical Review, Vol. 30, Issue 3 https://doi.org/10.1103/physrev.30.232	journal	September 1927
The Diffraction of X-Rays in Glass Warren, B. E. Physical Review, Vol. 45, Issue 10 https://doi.org/10.1103/physrev.45.657	journal	May 1934
Structure Factor and Radial Distribution Function for Liquid Argon at 85 °K Yarnell, J. L.; Katz, M. J.; Wenzel, R. G. Physical Review A, Vol. 7, Issue 6 https://doi.org/10.1103/physreva.7.2130	journal	June 1973
Systematic study of the glass transition in polyhydric alcohols Nakanishi, Masahiro; Nozaki, Ryusuke Physical Review E, Vol. 83, Issue 5 https://doi.org/10.1103/physreve.83.051503	journal	May 2011
Model of the cooperative rearranging region for polyhydric alcohols Nakanishi, Masahiro; Nozaki, Ryusuke Physical Review E, Vol. 84, Issue 1 https://doi.org/10.1103/physreve.84.011503	journal	July 2011
Exact Solution of the Percus-Yevick Integral Equation for Hard Spheres Wertheim, M. S. Physical Review Letters, Vol. 10, Issue 8 https://doi.org/10.1103/physrevlett.10.321	journal	April 1963
Intensity of diffracted intensities Brown, P. J.; Fox, A. G.; Maslen, E. N. International Tables for Crystallography, p. 554-595 https://doi.org/10.1107/97809553602060000600	book	October 2006
PDFgetX2: a GUI-driven program to obtain the pair distribution function from X-ray powder diffraction data Qiu, Xiangyun; Thompson, Jeroen W.; Billinge, Simon J. L. Journal of Applied Crystallography, Vol. 37, Issue 4, p. 678-678 https://doi.org/10.1107/s0021889804011744	journal	July 2004
Determination of Liquid Structures of the Primary Alcohols Methanol, Ethanol, 1-Propanol, 1-Butanol and 1-Octanol by X-ray Scattering Vahvaselkä, K. S.; Serimaa, R.; Torkkeli, M. Journal of Applied Crystallography, Vol. 28, Issue 2 https://doi.org/10.1107/s0021889894010149	journal	April 1995
An analytical method of computation of radial distribution functions at large distances for liquids and amorphous substances Korsunsky, V. I.; Naberukhin, Yu. I. Acta Crystallographica Section A, Vol. 36, Issue 1 https://doi.org/10.1107/s056773948000006x	journal	January 1980
The crystal structure of xylitol Kim, H. S.; Jeffrey, G. A. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 25, Issue 12 https://doi.org/10.1107/s0567740869006133	journal	December 1969
Determination of the crystal structure of the A form of D-glucitol by neutron and X-ray diffraction Park, Y. J.; Jeffrey, G. A.; Hamilton, W. C. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 27, Issue 12 https://doi.org/10.1107/s0567740871005934	journal	December 1971
NXFit : a program for simultaneously fitting X-ray and neutron diffraction pair-distribution functions to provide optimized structural parameters Pickup, David; Moss, Robert; Newport, Robert Journal of Applied Crystallography, Vol. 47, Issue 5 https://doi.org/10.1107/s160057671401824x	journal	September 2014
Formation of Glasses from Liquids and Biopolymers Angell, C. A. Science, Vol. 267, Issue 5206 https://doi.org/10.1126/science.267.5206.1924	journal	March 1995
Fifth-order susceptibility unveils growth of thermodynamic amorphous order in glass-formers Albert, S.; Bauer, T.; Michl, M. Science, Vol. 352, Issue 6291 https://doi.org/10.1126/science.aaf3182	journal	June 2016
Observation of a Hydrogen-Bonded 3D Structure of Crystalline Glycerol Kusukawa, Takahiro; Niwa, Genki; Sasaki, Takato Bulletin of the Chemical Society of Japan, Vol. 86, Issue 3 https://doi.org/10.1246/bcsj.20120300	journal	March 2013
The X-ray Structure Factor of Liquid Glycerol Soltwisch, M.; Steffen, B. Zeitschrift für Naturforschung A, Vol. 36, Issue 10 https://doi.org/10.1515/zna-1981-1004	journal	October 1981

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Title: Structures of glass-forming liquids by x-ray scattering: Glycerol, xylitol, and D-sorbitol

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