Title: Intermolecular correlations of liquid and glassy CS₂ studied by synchrotron radiation x-ray diffraction

Abstract

How is the orientation of molecular liquids ordered on cooling? What are the basic structures of molecular glasses, e.g., close to the crystalline structure or some special structures such as icosahedral cluster? These are long-standing questions in liquid and glass physics. Here, we have constructed a novel cryostat to prepare simple molecular glasses by vapor deposition and performed in situ synchrotron radiation x-ray diffraction experiments. The glassy state of a simple molecule CS₂, which cannot be vitrified by normal liquid quenching, was successfully prepared with this instrument, and its diffraction data were collected in a wide Q-range of 0.16–25.7 Å^-1 with a high-energy diffractometer at BL04B2, SPring-8. The diffraction data of liquid CS₂ were also recorded in a wide temperature range of 160–300 K. These diffraction data were analyzed with molecular dynamics simulations and reverse Monte Carlo modelings to investigate orientational correlation. From the obtained 3D structure models, the orientational correlation between neighboring CS₂ molecules was investigated quantitatively as a function of temperature. At room temperature, the parallel and T-shaped arrangements are preferred for the nearest neighbor correlation. On cooling, these arrangements are developed gradually, and its rate became prominent below the melting temperature (162 K). In the glassy state,more » the slipped-parallel arrangement is dominant as well as the T-shaped arrangement. Both arrangements appear in the CS₂ crystal, indicating that the structure of glassy CS₂ is close to that of crystalline CS₂.« less

Authors:

Mizuno, Yuki  ^[1];

• Search DOE PAGES for author "Mizuno, Yuki"
• Search DOE PAGES for ORCID "0000-0002-8543-7070"

Zhao, Yuansheng  ^[2];

• Search DOE PAGES for author "Zhao, Yuansheng"
• Search DOE PAGES for ORCID "0000-0002-0362-4092"

Akiba, Hiroshi ^[2]; Kohara, Shinji  ^[3];

• Search DOE PAGES for author "Kohara, Shinji"
• Search DOE PAGES for ORCID "0000-0001-9596-2680"

Ohara, Koji  ^[4];

• Search DOE PAGES for author "Ohara, Koji"
• Search DOE PAGES for ORCID "0000-0002-3134-512X"

Tucker, Matthew G.  ^[5];

• Search DOE PAGES for author "Tucker, Matthew G."
• Search DOE PAGES for ORCID "0000-0002-2891-7086"

McDonnell, Marshall T. ^[5]; Yamamuro, Osamu  ^[2]

• Search DOE PAGES for author "Yamamuro, Osamu"
• Search DOE PAGES for ORCID "0000-0002-5456-8932"

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+ Show Author Affiliations

1. Univ. of Tokyo (Japan); Japan Synchrotron Radiation Research Institute, Sayo, Hyogo (Japan)
2. Univ. of Tokyo (Japan)
3. National Institute for Materials Science (NIMS), Tsukuba (Japan)
4. Japan Synchrotron Radiation Research Institute, Sayo, Hyogo (Japan)
5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Publication Date:

Wed Jan 19 00:00:00 EST 2022

Research Org.:

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:

USDOE

OSTI Identifier:

1879944

Grant/Contract Number:  

AC05-00OR22725

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Chemical Physics

Additional Journal Information:

Journal Volume: 156; Journal Issue: 3; Journal ID: ISSN 0021-9606

Publisher:

American Institute of Physics (AIP)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; vapor deposition; diffractometers; molecular dynamics; glass transitions; molecular liquids; x-ray diffraction; neutron scattering; crystal structure; synchrotron radiation