論文

査読有り
2016年3月

Thermodynamic Stability of Ice II and Its Hydrogen-Disordered Counterpart: Role of Zero-Point Energy

JOURNAL OF PHYSICAL CHEMISTRY B
  • Tatsuya Nakamura
  • ,
  • Masakazu Matsumoto
  • ,
  • Takuma Yagasaki
  • ,
  • Hideki Tanaka

120
8
開始ページ
1843
終了ページ
1848
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1021/acs.jpcb.5b09544
出版者・発行元
AMER CHEMICAL SOC

We investigate why no hydrogen-disordered form of ice II has been found in nature despite the fact that most of hydrogen-ordered ices have hydrogen-disordered counterparts. The thermodynamic stability of a set of hydrogen-ordered ice II variants relative to ice II is evaluated theoretically. It is found that ice II is more stable than the disordered variants so generated as to satisfy the simple ice rule due to the lower zero point energy as well as the pair interaction energy. The residual entropy of the disordered ice II phase gradually compensates the unfavorable free energy with increasing temperature. The crossover, however, occurs at a high temperature well above the melting point of ice III. Consequently, the hydrogen-disordered phase does not exist in nature. The thermodynamic stability of partially hydrogen-disordered ices is also scrutinized by examining the free-energy components of several variants obtained by systematic inversion of OH directions in ice II. The potential energy of one variant is lower than that of the ice II structure, but its Gibbs free energy is slightly higher than that of ice II due to the zero-point energy. The slight difference in the thermodynamic stability leaves the possibility of the partial hydrogen-disorder in real ice II.

Web of Science ® 被引用回数 : 13

リンク情報
DOI
https://doi.org/10.1021/acs.jpcb.5b09544
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000371562700049&DestApp=WOS_CPL
URL
http://www.scopus.com/inward/record.url?eid=2-s2.0-84960157218&partnerID=MN8TOARS
URL
http://orcid.org/0000-0002-6799-6813

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