Effects of Confinement and Pressure on Vibrational Behavior of Nano-confined Propane

Gautam, Siddharth; Kolesnikov, Alexander I.; Rother, Gernot; Dai, Sheng; Qiao, Zhen-An; Cole, David R.

doi:10.1021/acs.jpca.8b05028

Title: Effects of Confinement and Pressure on Vibrational Behavior of Nano-confined Propane

Journal Article · Tue Jul 24 00:00:00 EDT 2018 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.8b05028· OSTI ID:1462830

Gautam, Siddharth ^[1];

^[2];

^[3];

^[3]; Qiao, Zhen-An ^[4]; Cole, David R. ^[1]

The Ohio State Univ., Columbus, OH (United States). School of Earth Sciences
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division; Jilin Univ., Changchun (China). State Key Lab. of Inorganic Synthesis and Preparative Chemistry and College of Chemistry

Fluids confined in nanopores exhibit significant deviations in their structure and dynamics from the bulk behavior. Although phase, structural and diffusive behaviors of confined fluids have been investigated and reported extensively, confinement effects on the vibrational properties are less understood. Here, we study the vibrational behavior of propane confined in 1.5 nm nanopores of MCM-41-S using inelastic neutron scattering (INS) and molecular dynamics (MD) simulations. Vibrational spectra have been obtained from INS data as functions of temperature and pressure. At ambient pressure, a strong quasielastic signal observed in the INS spectrum at 80 K suggests that confined propane remains liquid below the bulk phase melting point of 85 K. The quasielastic signal is heavily suppressed when either the pressure is increased to 1 kbar, or the temperature is lowered to 30 K, indicating solidification of pore-confined propane. Confinement in MCM-41-S pores results in a glass-like state of propane that exhibits a relatively featureless low-energy vibrational spectrum compared to the bulk crystalline propane. Increasing the pressure to 3 kbar results in hardening of the intermolecular and methyl torsional modes. The INS data are used for estimating the isochoric specific heat of confined propane, which is compared with the specific heat of bulk propane reported in literature. Data from MD simulations is used to calculate the vibrational power spectra that agree qualitatively with the experimental data. Simulation data also suggests a reduction in the structural ordering (positional, orientational and intramolecular) of propane under confinement.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division

Contributing Organization:: Science and Technology Facilities Council (STFC), Daresbury (United Kingdom). Daresbury Lab.; Rensselaer Polytechnic Inst., Troy, NY (United States)

Grant/Contract Number:: AC05-00OR22725; SC0006878

OSTI ID:: 1462830

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. TBD, Issue TBD; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 16 works

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References (52)

Structure and Dynamics of Confined C-O-H Fluids Relevant to the Subsurface: Application of Magnetic Resonance, Neutron Scattering, and Molecular Dynamics Simulations Gautam, Siddharth S.; Ok, Salim; Cole, David R. Frontiers in Earth Science, Vol. 5 https://doi.org/10.3389/feart.2017.00043	journal	June 2017
Anomalous Behavior of Proton Zero Point Motion in Water Confined in Carbon Nanotubes Reiter, G.; Burnham, C.; Homouz, D. Physical Review Letters, Vol. 97, Issue 24 https://doi.org/10.1103/PhysRevLett.97.247801	journal	December 2006
Quantum Tunneling of Water in Beryl: A New State of the Water Molecule Kolesnikov, Alexander I.; Reiter, George F.; Choudhury, Narayani Physical Review Letters, Vol. 116, Issue 16 https://doi.org/10.1103/PhysRevLett.116.167802	journal	April 2016
Local structure and density fluctuations in confined fluids Nygård, Kim Current Opinion in Colloid & Interface Science, Vol. 22 https://doi.org/10.1016/j.cocis.2016.02.005	journal	April 2016
Effects of confinement on freezing and melting Alba-Simionesco, C.; Coasne, B.; Dosseh, G. Journal of Physics: Condensed Matter, Vol. 18, Issue 6 https://doi.org/10.1088/0953-8984/18/6/R01	journal	January 2006
Effect of Confinement on Pressure/Volume/Temperature Properties of Hydrocarbons in Shale Reservoirs Pitakbunkate, Termpan; Balbuena, Perla B.; Moridis, George J. SPE Journal, Vol. 21, Issue 02 https://doi.org/10.2118/170685-PA	journal	April 2016
Motions and Relaxations of Confined Liquids Granick, S. Science, Vol. 253, Issue 5026 https://doi.org/10.1126/science.253.5026.1374	journal	September 1991
High H ₂ Sorption Energetics in Zeolitic Imidazolate Frameworks Pham, Tony; Forrest, Katherine A.; Furukawa, Hiroyasu The Journal of Physical Chemistry C, Vol. 121, Issue 3 https://doi.org/10.1021/acs.jpcc.6b11466	journal	January 2017
Investigating H ₂ Sorption in a Fluorinated Metal–Organic Framework with Small Pores Through Molecular Simulation and Inelastic Neutron Scattering Forrest, Katherine A.; Pham, Tony; Georgiev, Peter A. Langmuir, Vol. 31, Issue 26 https://doi.org/10.1021/acs.langmuir.5b01664	journal	February 2015
Diffusive and rotational dynamics of condensed n-H ₂ confined in MCM-41 Prisk, T. R.; Bryan, M. S.; Sokol, P. E. Phys. Chem. Chem. Phys., Vol. 16, Issue 33 https://doi.org/10.1039/C4CP02281E	journal	January 2014
Properties of immobile hydrogen confined in microporous carbon Bahadur, Jitendra; Contescu, Cristian I.; Ramirez-Cuesta, Anibal J. Carbon, Vol. 117 https://doi.org/10.1016/j.carbon.2017.03.007	journal	June 2017
Restricted dynamics of molecular hydrogen confined in activated carbon nanopores Contescu, Cristian I.; Saha, Dipendu; Gallego, Nidia C. Carbon, Vol. 50, Issue 3 https://doi.org/10.1016/j.carbon.2011.10.016	journal	March 2012
Phases of superfluid helium in smooth cylindrical pores Prisk, Timothy R.; Das, Narayan C.; Diallo, Souleymane O. Physical Review B, Vol. 88, Issue 1 https://doi.org/10.1103/PhysRevB.88.014521	journal	July 2013
Subcontinuum mass transport of condensed hydrocarbons in nanoporous media Falk, Kerstin; Coasne, Benoit; Pellenq, Roland Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms7949	journal	April 2015
Shales at all scales: Exploring coupled processes in mudrocks Ilgen, Anastasia G.; Heath, Jason E.; Akkutlu, I. Yucel Earth-Science Reviews, Vol. 166 https://doi.org/10.1016/j.earscirev.2016.12.013	journal	March 2017
Molecular self-diffusion of methane in zeolite ZSM-5 by quasi-elastic neutron scattering and nuclear magnetic resonance pulsed field gradient technique Jobic, Hervé; Bée, Marc; Caro, Jürgen Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 85, Issue 12 https://doi.org/10.1039/f19898504201	journal	January 1989
Molecular dynamics simulation of propane and methane in silicalite Nicholas, John B.; Trouw, Frans R.; Mertz, John E. The Journal of Physical Chemistry, Vol. 97, Issue 16 https://doi.org/10.1021/j100118a035	journal	April 1993
Unidirectional and Single-File Diffusion of Molecules in One-Dimensional Channel Systems. A Quasi-Elastic Neutron Scattering Study Jobic, Hervé; Hahn, Karsten; Kärger, Jörg The Journal of Physical Chemistry B, Vol. 101, Issue 30 https://doi.org/10.1021/jp970773i	journal	July 1997
Dynamics of methane molecules in porous TiO ₂ Krasnov, I. A.; Asmussen, B.; Gutt, C. Journal of Physics: Condensed Matter, Vol. 12, Issue 8 https://doi.org/10.1088/0953-8984/12/8/304	journal	February 2000
Concentration dependence of transport diffusion of ethane in silicalite: A comparison between neutron scattering experiments and atomically detailed simulations Chong, Shang-Shan; Jobic, Hervé; Plazanet, Marie Chemical Physics Letters, Vol. 408, Issue 1-3 https://doi.org/10.1016/j.cplett.2005.04.023	journal	June 2005
Structural and dynamic properties of confined ethane in AlPO4-5 model microporous aluminophosphate: Does the predicted quasi-(1D) phase transition exist? Coulomb, Jean-Paul; Floquet, Nicole; André, Gilles Microporous and Mesoporous Materials, Vol. 141, Issue 1-3 https://doi.org/10.1016/j.micromeso.2009.11.010	journal	May 2011
Role of Confinement on Adsorption and Dynamics of Ethane and an Ethane–CO ₂ Mixture in Mesoporous CPG Silica Patankar, Sumant; Gautam, Siddharth; Rother, Gernot The Journal of Physical Chemistry C, Vol. 120, Issue 9 https://doi.org/10.1021/acs.jpcc.5b09984	journal	February 2016
Location dependent orientational structure and dynamics of ethane in ZSM5 Gautam, Siddharth; Liu, Tingting; Patankar, Sumant Chemical Physics Letters, Vol. 648 https://doi.org/10.1016/j.cplett.2016.02.021	journal	March 2016
Dynamics of ethane and propane in zeolite ZSM-5 studied by quasi-elastic neutron scattering Jobic, Hervé; Bée, Marc; Kearley, Gordon J. Zeolites, Vol. 12, Issue 2 https://doi.org/10.1016/0144-2449(92)90075-Z	journal	February 1992
Molecular dynamics simulation study of meso-confined propane in TiO2 Gautam, Siddharth; Cole, David Chemical Physics, Vol. 458 https://doi.org/10.1016/j.chemphys.2015.07.012	journal	September 2015
Dynamics of Propane in Nanoporous Silica Aerogel: A Quasielastic Neutron Scattering Study Gautam, Siddharth; Liu, Tingting; Rother, Gernot The Journal of Physical Chemistry C, Vol. 119, Issue 32 https://doi.org/10.1021/acs.jpcc.5b03444	journal	July 2015
Molecular dynamics simulations of propane in slit shaped silica nano-pores: direct comparison with quasielastic neutron scattering experiments Gautam, Siddharth; Le, Thu; Striolo, Alberto Physical Chemistry Chemical Physics, Vol. 19, Issue 48 https://doi.org/10.1039/C7CP05715F	journal	January 2017
Effect of molecular shape on rotation under severe confinement Dhiman, I.; Bhowmik, D.; Shrestha, Utsab R. Chemical Engineering Science, Vol. 180 https://doi.org/10.1016/j.ces.2018.01.027	journal	April 2018
Propane on Titan Roe, H. G.; Greathouse, T. K.; Richter, M. J. The Astrophysical Journal, Vol. 597, Issue 1 https://doi.org/10.1086/379816	journal	October 2003
Why Propane? Podsiadło, Marcin; Olejniczak, Anna; Katrusiak, Andrzej The Journal of Physical Chemistry C, Vol. 117, Issue 9 https://doi.org/10.1021/jp311747m	journal	February 2013
Thermodynamic Study on Simple Molecular Glasses Yamamuro, Osamu; Tatsumi, Soichi Nihon Reoroji Gakkaishi, Vol. 40, Issue 3 https://doi.org/10.1678/rheology.40.137	journal	January 2012
Glass Transition, Crystallization, Melting, and Decomposition of Nanoconfined Propane Films at Cryogenic Temperatures Souda, Ryutaro The Journal of Physical Chemistry C, Vol. 120, Issue 31 https://doi.org/10.1021/acs.jpcc.6b05299	journal	July 2016
Methyl Libration in Propane Measured with Neutron Inelastic Scattering Grant, David M.; Pugmire, Ronald J.; Livingston, Robert C. The Journal of Chemical Physics, Vol. 52, Issue 9 https://doi.org/10.1063/1.1673668	journal	May 1970
First high resolution analysis of the ν21 band of propane CH3CH2CH3 at 921.382cm−1: Evidence of large amplitude tunneling effects Perrin, A.; Kwabia-Tchana, F.; Flaud, J. M. Journal of Molecular Spectroscopy, Vol. 315 https://doi.org/10.1016/j.jms.2015.02.010	journal	September 2015
A Review: Fundamental Aspects of Silicate Mesoporous Materials ALOthman, Zeid Materials, Vol. 5, Issue 12 https://doi.org/10.3390/ma5122874	journal	December 2012
A comparison of four direct geometry time-of-flight spectrometers at the Spallation Neutron Source Stone, M. B.; Niedziela, J. L.; Abernathy, D. L. Review of Scientific Instruments, Vol. 85, Issue 4 https://doi.org/10.1063/1.4870050	journal	April 2014
SEQUOIA: A Newly Operating Chopper Spectrometer at the SNS Granroth, G. E.; Kolesnikov, A. I.; Sherline, T. E. Journal of Physics: Conference Series, Vol. 251 https://doi.org/10.1088/1742-6596/251/1/012058	journal	November 2010
Mantid—Data analysis and visualization package for neutron scattering and $μ$ SR experiments Arnold, O.; Bilheux, J. C.; Borreguero, J. M. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 764 https://doi.org/10.1016/j.nima.2014.07.029	journal	November 2014
DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6 https://doi.org/10.6028/jres.114.025	journal	November 2009
DL_POLY_3: new dimensions in molecular dynamics simulations via massive parallelism Todorov, Ilian T.; Smith, William; Trachenko, Kostya Journal of Materials Chemistry, Vol. 16, Issue 20, p. 1911-1918 https://doi.org/10.1039/b517931a	journal	January 2006
Factors affecting molecular dynamics simulated vitreous silica structures Huff, Norman T.; Demiralp, Ersan; Çagin, Tahir Journal of Non-Crystalline Solids, Vol. 253, Issue 1-3 https://doi.org/10.1016/S0022-3093(99)00349-X	journal	August 1999
Propane simulated in silica pores: Adsorption isotherms, molecular structure, and mobility Le, Thu; Striolo, Alberto; Cole, David R. Chemical Engineering Science, Vol. 121 https://doi.org/10.1016/j.ces.2014.08.022	journal	January 2015
Propane–Water Mixtures Confined within Cylindrical Silica Nanopores: Structural and Dynamical Properties Probed by Molecular Dynamics Le, Tran Thi Bao; Striolo, Alberto; Gautam, Siddharth S. Langmuir, Vol. 33, Issue 42 https://doi.org/10.1021/acs.langmuir.7b03093	journal	September 2017
The Melting Point Alternation in the Short-Chainn-Alkanes: Single-Crystal X-Ray Analyses of Propane at 30 K and ofn-Butane ton-Nonane at 90 K Boese, Roland; Weiss, Hans-Christoph; Bläser, Dieter Angewandte Chemie International Edition, Vol. 38, Issue 7 https://doi.org/10.1002/(SICI)1521-3773(19990401)38:7<988::AID-ANIE988>3.0.CO;2-0	journal	April 1999
Thermal Conductivity of MgO Periclase from Equilibrium First Principles Molecular Dynamics de Koker, Nico Physical Review Letters, Vol. 103, Issue 12 https://doi.org/10.1103/PhysRevLett.103.125902	journal	September 2009
Global phase diagrams for freezing in porous media Radhakrishnan, Ravi; Gubbins, Keith E.; Sliwinska-Bartkowiak, Malgorzata The Journal of Chemical Physics, Vol. 116, Issue 3 https://doi.org/10.1063/1.1426412	journal	January 2002
Neutron spectroscopy of magnesium dihydride Kolesnikov, A. I.; Antonov, V. E.; Efimchenko, V. S. Journal of Alloys and Compounds, Vol. 509 https://doi.org/10.1016/j.jallcom.2010.10.156	journal	September 2011
Hindered Rotation of the Methyl Groups in Propane. The Heat Capacity, Vapor Pressure, Heats of Fusion and Vaporization of Propane. Entropy and Density of the Gas Kemp, J. D.; Egan, Clark J. Journal of the American Chemical Society, Vol. 60, Issue 7 https://doi.org/10.1021/ja01274a001	journal	July 1938
Specific heats of saturated and compressed liquid propane Goodwin, R. D. Journal of Research of the National Bureau of Standards, Vol. 83, Issue 5 https://doi.org/10.6028/jres.083.031	journal	September 1978
Excess heat capacities due to the low-energy excitations of molecular glasses: An approach using the soft potential model Lindqvist, Anna; Yamamuro, Osamu; Tsukushi, Itaru The Journal of Chemical Physics, Vol. 107, Issue 13 https://doi.org/10.1063/1.474873	journal	October 1997
Inelastic neutron scattering study of low-energy excitations in vapor-deposited glassy propylene Yamamuro, Osamu; Tsukushi, Itaru; Matsuo, Takasuke The Journal of Chemical Physics, Vol. 106, Issue 8 https://doi.org/10.1063/1.473045	journal	February 1997
Transferable Potentials for Phase Equilibria. 1. United-Atom Description of n-Alkanes Martin, Marcus G.; Siepmann, J. Ilja https://doi.org/10.1021/jp972543+		March 1998

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