Dynamics in the Plastic Crystalline Phases of Cyclohexanol and Cyclooctanol Studied by Quasielastic Neutron Scattering

Novak, Eric C.; Jalarvo, Niina H.; Gupta, Sudipta; Hong, Kunlun; Förster, Stephan; Egami, Takeshi; Ohl, M.

doi:10.1021/acs.jpcb.8b03448

Title: Dynamics in the Plastic Crystalline Phases of Cyclohexanol and Cyclooctanol Studied by Quasielastic Neutron Scattering

Abstract

Plastic crystals are a promising candidate for solid state ionic conductors. In this work, quasielastic neutron scattering is employed to investigate the center of mass diffusive motions in two types of plastic crystalline cyclic alcohols: cyclohexanol and cyclooctanol. Two separate motions are observed which are attributed to long-range translational diffusion (α-process) and cage rattling (fast β-process). Residence times and diffusion coefficients are calculated for both processes, along with the confinement distances for the cage rattling. In addition, a binary mixture of these two materials is measured to understand how the dynamics change when a second type of molecule is added to the matrix. It is observed that, upon the addition of the larger cyclooctanol molecules into the cyclohexanol solution, the cage size decreases, which causes a decrease in the observed diffusion rates for both the α- and fast β-processes.

Authors:

^[1];

^[2];

^[3];

^[4];

^[5]; Egami, Takeshi ^[6]; Ohl, M. ^[5]

University of Tennessee, Knoxville, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Forschungszentrum Jülich GmbH, Jülich (Germany)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Forschungszentrum Jülich GmbH, Jülich (Germany)
Louisiana State University, Baton Rouge, LA (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); University of Tennessee, Knoxville, TN (United States)
Forschungszentrum Jülich GmbH, Jülich (Germany)
University of Tennessee, Knoxville, TN (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Publication Date:: 2018-05-18

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Louisiana State Univ., Baton Rouge, LA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1526395

Alternate Identifier(s):: OSTI ID: 1673753

Grant/Contract Number:: AC05-00OR22725; SC0012432

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

Additional Journal Information:: Journal Volume: 122; Journal Issue: 23; Journal ID: ISSN 1520-6106

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Transport properties; Mixtures; Diffusion; Phase transitions; Molecules; Transport properties, Mixtures, Diffusion, Phase transitions, Molecules

Citation Formats


                    Novak, Eric C., Jalarvo, Niina H., Gupta, Sudipta, Hong, Kunlun, Förster, Stephan, Egami, Takeshi, and Ohl, M. Dynamics in the Plastic Crystalline Phases of Cyclohexanol and Cyclooctanol Studied by Quasielastic Neutron Scattering.  United States: N. p., 2018. 
Web.  doi:10.1021/acs.jpcb.8b03448.

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                    Novak, Eric C., Jalarvo, Niina H., Gupta, Sudipta, Hong, Kunlun, Förster, Stephan, Egami, Takeshi, & Ohl, M. Dynamics in the Plastic Crystalline Phases of Cyclohexanol and Cyclooctanol Studied by Quasielastic Neutron Scattering.  United States.  https://doi.org/10.1021/acs.jpcb.8b03448

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                    Novak, Eric C., Jalarvo, Niina H., Gupta, Sudipta, Hong, Kunlun, Förster, Stephan, Egami, Takeshi, and Ohl, M. Fri .  
"Dynamics in the Plastic Crystalline Phases of Cyclohexanol and Cyclooctanol Studied by Quasielastic Neutron Scattering".  United States.  https://doi.org/10.1021/acs.jpcb.8b03448.  https://www.osti.gov/servlets/purl/1526395.

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@article{osti_1526395,

  title        = {Dynamics in the Plastic Crystalline Phases of Cyclohexanol and Cyclooctanol Studied by Quasielastic Neutron Scattering},

  author       = {Novak, Eric C. and Jalarvo, Niina H. and Gupta, Sudipta and Hong, Kunlun and Förster, Stephan and Egami, Takeshi and Ohl, M.},

  abstractNote = {Plastic crystals are a promising candidate for solid state ionic conductors. In this work, quasielastic neutron scattering is employed to investigate the center of mass diffusive motions in two types of plastic crystalline cyclic alcohols: cyclohexanol and cyclooctanol. Two separate motions are observed which are attributed to long-range translational diffusion (α-process) and cage rattling (fast β-process). Residence times and diffusion coefficients are calculated for both processes, along with the confinement distances for the cage rattling. In addition, a binary mixture of these two materials is measured to understand how the dynamics change when a second type of molecule is added to the matrix. It is observed that, upon the addition of the larger cyclooctanol molecules into the cyclohexanol solution, the cage size decreases, which causes a decrease in the observed diffusion rates for both the α- and fast β-processes.},

  doi          = {10.1021/acs.jpcb.8b03448},

  journal      = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},

  number       = 23,

  volume       = 122,

  place        = {United States},

  year         = {2018},

  month        = {5}

}

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Figure 1: (a) QENS data for OCT at Q = 1.0 Å^-1 and temperatures 230 K, 240 K, 270 K, and 280 K. The solid lines are a fit of Eq. 1 and the dotted-dashed line is the resolution function. The insert displays all the fit components for T =more »

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