Atomic and Electronic Structure in MgO-SiO2

Yuta Shuseki; Shinji Kohara; Tomoaki Kaneko; Keitaro Sodeyama; Yohei Onodera; Chihiro Koyama; Atsunobu Masuno; Shunta Sasaki; Shohei Hatano; Motoki Shiga; Ippei Obayashi; Yasuaki Hiraoka; Junpei T. Okada; Akitoshi Mizuno; Yuki Watanabe; Yui Nakata; Koji Ohara; Motohiko Murakami; Matthew G. Tucker; Marshall T. McDonnell; Hirohisa Oda; Takehiko Ishikawa

doi:10.1021/acs.jpca.3c05561

Atomic and Electronic Structure in MgO-SiO₂

Yuta Shuseki, Shinji Kohara, Tomoaki Kaneko, Keitaro Sodeyama, Yohei Onodera, Chihiro Koyama, Atsunobu Masuno, Shunta Sasaki, Shohei Hatano, Motoki Shiga, Ippei Obayashi, Yasuaki Hiraoka, Junpei T. Okada, Akitoshi Mizuno, Yuki Watanabe, Yui Nakata, Koji Ohara, Motohiko Murakami, Matthew G. Tucker, Marshall T. McDonnellHirohisa Oda, Takehiko Ishikawa

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

Understanding disordered structure is difficult due to insufficient information in experimental data. Here, we overcome this issue by using a combination of diffraction and simulation to investigate oxygen packing and network topology in glassy (g-) and liquid (l-) MgO-SiO₂ based on a comparison with the crystalline topology. We find that packing of oxygen atoms in Mg₂SiO₄ is larger than that in MgSiO₃, and that of the glasses is larger than that of the liquids. Moreover, topological analysis suggests that topological similarity between crystalline (c)- and g-(l-) Mg₂SiO₄ is the signature of low glass-forming ability (GFA), and high GFA g-(l-) MgSiO₃ shows a unique glass topology, which is different from c-MgSiO₃. We also find that the lowest unoccupied molecular orbital (LUMO) is a free electron-like state at a void site of magnesium atom arising from decreased oxygen coordination, which is far away from crystalline oxides in which LUMO is occupied by oxygen’s 3s orbital state in g- and l-MgO-SiO₂, suggesting that electronic structure does not play an important role to determine GFA. We finally concluded the GFA of MgO-SiO₂ binary is dominated by the atomic structure in terms of network topology.

Original language	English
Pages (from-to)	716-726
Number of pages	11
Journal	Journal of Physical Chemistry A
Volume	128
Issue number	4
DOIs	https://doi.org/10.1021/acs.jpca.3c05561
State	Published - Feb 1 2024

Funding

The synchrotron radiation experiments were performed with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (proposal nos. 2018A1096 and 2022A1074). The neutron data were collected on the NOMAD instrument at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This research was supported by JSPS Grant-in-Aid for Transformative Research Areas (A) “Hyper-Ordered Structures Science” Grant Numbers 20H05878 (to M.S. and S.K.), 20H05881 (to S.K. and Y.O.), 20H05882 (to T.I.), 20H05884 (to M.S.), and KAKENIHI Grant Number 19K05648 (to Y.O.)). Discussion with Yuji Higo is gratefully appreciated.

Funders	Funder number
Japan Society for the Promotion of Science	20H05881, 20H05882, 20H05884, 19K05648, 20H05878

Access to Document

10.1021/acs.jpca.3c05561

Cite this

Shuseki, Y., Kohara, S., Kaneko, T., Sodeyama, K., Onodera, Y., Koyama, C., Masuno, A., Sasaki, S., Hatano, S., Shiga, M., Obayashi, I., Hiraoka, Y., Okada, J. T., Mizuno, A., Watanabe, Y., Nakata, Y., Ohara, K., Murakami, M., Tucker, M. G., ... Ishikawa, T. (2024). Atomic and Electronic Structure in MgO-SiO₂. Journal of Physical Chemistry A, 128(4), 716-726. https://doi.org/10.1021/acs.jpca.3c05561

@article{12d13483fdeb440998647a52355e5fc1,

title = "Atomic and Electronic Structure in MgO-SiO2",

abstract = "Understanding disordered structure is difficult due to insufficient information in experimental data. Here, we overcome this issue by using a combination of diffraction and simulation to investigate oxygen packing and network topology in glassy (g-) and liquid (l-) MgO-SiO2 based on a comparison with the crystalline topology. We find that packing of oxygen atoms in Mg2SiO4 is larger than that in MgSiO3, and that of the glasses is larger than that of the liquids. Moreover, topological analysis suggests that topological similarity between crystalline (c)- and g-(l-) Mg2SiO4 is the signature of low glass-forming ability (GFA), and high GFA g-(l-) MgSiO3 shows a unique glass topology, which is different from c-MgSiO3. We also find that the lowest unoccupied molecular orbital (LUMO) is a free electron-like state at a void site of magnesium atom arising from decreased oxygen coordination, which is far away from crystalline oxides in which LUMO is occupied by oxygen{\textquoteright}s 3s orbital state in g- and l-MgO-SiO2, suggesting that electronic structure does not play an important role to determine GFA. We finally concluded the GFA of MgO-SiO2 binary is dominated by the atomic structure in terms of network topology.",

author = "Yuta Shuseki and Shinji Kohara and Tomoaki Kaneko and Keitaro Sodeyama and Yohei Onodera and Chihiro Koyama and Atsunobu Masuno and Shunta Sasaki and Shohei Hatano and Motoki Shiga and Ippei Obayashi and Yasuaki Hiraoka and Okada, {Junpei T.} and Akitoshi Mizuno and Yuki Watanabe and Yui Nakata and Koji Ohara and Motohiko Murakami and Tucker, {Matthew G.} and McDonnell, {Marshall T.} and Hirohisa Oda and Takehiko Ishikawa",

note = "Publisher Copyright: {\textcopyright} 2024 The Authors. Published by American Chemical Society.",

year = "2024",

month = feb,

day = "1",

doi = "10.1021/acs.jpca.3c05561",

language = "English",

volume = "128",

pages = "716--726",

journal = "Journal of Physical Chemistry A",

issn = "1089-5639",

publisher = "American Chemical Society",

number = "4",

}

Shuseki, Y, Kohara, S, Kaneko, T, Sodeyama, K, Onodera, Y, Koyama, C, Masuno, A, Sasaki, S, Hatano, S, Shiga, M, Obayashi, I, Hiraoka, Y, Okada, JT, Mizuno, A, Watanabe, Y, Nakata, Y, Ohara, K, Murakami, M, Tucker, MG , McDonnell, MT, Oda, H & Ishikawa, T 2024, 'Atomic and Electronic Structure in MgO-SiO₂', Journal of Physical Chemistry A, vol. 128, no. 4, pp. 716-726. https://doi.org/10.1021/acs.jpca.3c05561

TY - JOUR

T1 - Atomic and Electronic Structure in MgO-SiO2

AU - Shuseki, Yuta

AU - Kohara, Shinji

AU - Kaneko, Tomoaki

AU - Sodeyama, Keitaro

AU - Onodera, Yohei

AU - Koyama, Chihiro

AU - Masuno, Atsunobu

AU - Sasaki, Shunta

AU - Hatano, Shohei

AU - Shiga, Motoki

AU - Obayashi, Ippei

AU - Hiraoka, Yasuaki

AU - Okada, Junpei T.

AU - Mizuno, Akitoshi

AU - Watanabe, Yuki

AU - Nakata, Yui

AU - Ohara, Koji

AU - Murakami, Motohiko

AU - Tucker, Matthew G.

AU - McDonnell, Marshall T.

AU - Oda, Hirohisa

AU - Ishikawa, Takehiko

PY - 2024/2/1

Y1 - 2024/2/1

N2 - Understanding disordered structure is difficult due to insufficient information in experimental data. Here, we overcome this issue by using a combination of diffraction and simulation to investigate oxygen packing and network topology in glassy (g-) and liquid (l-) MgO-SiO2 based on a comparison with the crystalline topology. We find that packing of oxygen atoms in Mg2SiO4 is larger than that in MgSiO3, and that of the glasses is larger than that of the liquids. Moreover, topological analysis suggests that topological similarity between crystalline (c)- and g-(l-) Mg2SiO4 is the signature of low glass-forming ability (GFA), and high GFA g-(l-) MgSiO3 shows a unique glass topology, which is different from c-MgSiO3. We also find that the lowest unoccupied molecular orbital (LUMO) is a free electron-like state at a void site of magnesium atom arising from decreased oxygen coordination, which is far away from crystalline oxides in which LUMO is occupied by oxygen’s 3s orbital state in g- and l-MgO-SiO2, suggesting that electronic structure does not play an important role to determine GFA. We finally concluded the GFA of MgO-SiO2 binary is dominated by the atomic structure in terms of network topology.

AB - Understanding disordered structure is difficult due to insufficient information in experimental data. Here, we overcome this issue by using a combination of diffraction and simulation to investigate oxygen packing and network topology in glassy (g-) and liquid (l-) MgO-SiO2 based on a comparison with the crystalline topology. We find that packing of oxygen atoms in Mg2SiO4 is larger than that in MgSiO3, and that of the glasses is larger than that of the liquids. Moreover, topological analysis suggests that topological similarity between crystalline (c)- and g-(l-) Mg2SiO4 is the signature of low glass-forming ability (GFA), and high GFA g-(l-) MgSiO3 shows a unique glass topology, which is different from c-MgSiO3. We also find that the lowest unoccupied molecular orbital (LUMO) is a free electron-like state at a void site of magnesium atom arising from decreased oxygen coordination, which is far away from crystalline oxides in which LUMO is occupied by oxygen’s 3s orbital state in g- and l-MgO-SiO2, suggesting that electronic structure does not play an important role to determine GFA. We finally concluded the GFA of MgO-SiO2 binary is dominated by the atomic structure in terms of network topology.

UR - http://www.scopus.com/inward/record.url?scp=85183509291&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.3c05561

DO - 10.1021/acs.jpca.3c05561

M3 - Article

AN - SCOPUS:85183509291

SN - 1089-5639

VL - 128

SP - 716

EP - 726

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

IS - 4

ER -

Atomic and Electronic Structure in MgO-SiO₂

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this