TY - JOUR
T1 - On the role of intermolecular vibrational motions for ice polymorphs I
T2 - Volumetric properties of crystalline and amorphous ices
AU - Tanaka, Hideki
AU - Yagasaki, Takuma
AU - Matsumoto, Masakazu
N1 - Funding Information:
The authors are grateful to Dr. O. Mishima for helpful discussion on the thermal expansivity of amorphous ices. This work was supported by JSPS KAKENHI Grant No. 17K19106, MEXT as “Priority Issue on Post-Kcomputer” (Development of new fundamental technologies for high-efficiency energy creation, conversion/storage and use), and Research Center for Computational Science, Okazaki, Japan, for providing computational resource.
Publisher Copyright:
© 2019 Author(s).
PY - 2019/9/21
Y1 - 2019/9/21
N2 - Intermolecular vibrations and volumetric properties are investigated using the quasiharmonic approximation with the TIP4P/2005, TIP4P/Ice, and SPC/E potential models for most of the known crystalline and amorphous ice forms that have hydrogen-disordering. The ice forms examined here cover low pressure ices (hexagonal and cubic ice I, XVI, and hypothetical dtc ice), medium pressure ices (III, IV, V, VI, XII, hydrogen-disordered variant of ice II), and high pressure ice (VII) as well as the low density and the high density amorphous forms. We focus on the thermal expansivities and the isothermal compressibilities in the low temperature regime over a wide range of pressures calculated via the intermolecular vibrational free energies. Negative thermal expansivity appears only in the low pressure ice forms. The sign of the thermal expansivity is elucidated in terms of the mode Grüneisen parameters of the low frequency intermolecular vibrational motions. Although the band structure for the low frequency region of the vibrational density of state in the medium pressure ice has a close resemblance to that in the low pressure ice, its response against volume variation is opposite. We reveal that the mixing of translational and rotational motions in the low frequency modes plays a crucial role in the appearance of the negative thermal expansivity in the low pressure ice forms. The medium pressure ices can be further divided into two groups in terms of the hydrogen-bond network flexibility, which is manifested in the properties on the molecular rearrangement against volume variation, notably the isothermal compressibility.
AB - Intermolecular vibrations and volumetric properties are investigated using the quasiharmonic approximation with the TIP4P/2005, TIP4P/Ice, and SPC/E potential models for most of the known crystalline and amorphous ice forms that have hydrogen-disordering. The ice forms examined here cover low pressure ices (hexagonal and cubic ice I, XVI, and hypothetical dtc ice), medium pressure ices (III, IV, V, VI, XII, hydrogen-disordered variant of ice II), and high pressure ice (VII) as well as the low density and the high density amorphous forms. We focus on the thermal expansivities and the isothermal compressibilities in the low temperature regime over a wide range of pressures calculated via the intermolecular vibrational free energies. Negative thermal expansivity appears only in the low pressure ice forms. The sign of the thermal expansivity is elucidated in terms of the mode Grüneisen parameters of the low frequency intermolecular vibrational motions. Although the band structure for the low frequency region of the vibrational density of state in the medium pressure ice has a close resemblance to that in the low pressure ice, its response against volume variation is opposite. We reveal that the mixing of translational and rotational motions in the low frequency modes plays a crucial role in the appearance of the negative thermal expansivity in the low pressure ice forms. The medium pressure ices can be further divided into two groups in terms of the hydrogen-bond network flexibility, which is manifested in the properties on the molecular rearrangement against volume variation, notably the isothermal compressibility.
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U2 - 10.1063/1.5119748
DO - 10.1063/1.5119748
M3 - Article
C2 - 31542026
AN - SCOPUS:85072533340
SN - 0021-9606
VL - 151
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 11
M1 - 114501
ER -