Phase-Transition Behaviors of Crystalline Hypophosphorous Acid and a Feasible Incommensurate Wave-like Array of the Proton Displacements from Each Center of Hydrogen Bonds along the 1-Dimensional Chain
Phase-Transition Behaviors of Crystalline Hypophosphorous Acid and a Feasible Incommensurate Wave-like Array of the Proton Displacements from Each Center of Hydrogen Bonds along the 1-Dimensional Chain
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结晶次磷酸的相变行为和一维链上每个氢键中心的质子位移的可行的不相称波状阵列
DOI：
10.1021/acs.jpcc.2c07061
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Kohei Ueda and Masaharu Oguni
中科院分区：
文献类型：
--
作者：
Masako Yokoyama;Ryohei Kishi;Yasutaka Kitagawa;西本拓史，角屋智史，三宅力優，小田丈志，西田純一，久保和也，田島裕之，川瀬毅，山田順一;Kohei Ueda and Masaharu Oguni
在20~306K温度范围内，用绝热量热法和介电测量相结合的方法研究了由强氢键链组成的结晶型次磷酸。热容曲线显示出随后的相变：210.4 K的二级相变，159K的一级相变，149K和139.4 K的两次相变。用实数编码遗传算法确定的基线热容估算了相变的总熵为0.35 J K~(-1)mol~(-1)。这一较小的值被解释为跃迁与形成氢键的质子的位移有关：即，当它们位于210.4 K以上的两个氧原子之间的中心时，质子移动到靠近其中一个氧原子的位置，其下方的键长扩大。介电常数与温度的关系不明显，在210K附近，表明(反)铁电性的存在。由此推测，在210.4 K以下，氢键链上质子的偏心位移呈现出波状和无公度的形态，称为其上方的正常晶格，在159K下锁定为波状的超晶格。
Crystalline hypophosphorous acid, composed of strongly hydrogen-bonded chains, was investigated by adiabatic calorimetry in a temperature range between 20 and 306 K and by dielectrometry as a supplemental means. The heat-capacity curve showed subsequent phase transitions: a second-order one at 210.4 K followed by a first-order one at 159 K and the other two ones at 149 and 139.4 K with decreasing temperature. The total entropy of the transitions was assessed to be 0.35 J K–1mol–1by using the baseline heat capacities that were determined by means of a real-coded genetic algorithm. The small value was interpreted as the transitions were associated with displacements of the protons forming hydrogen bonds: namely, while they are located at the center between two oxygen atoms above 210.4 K, the protons are displaced close to one of the oxygen atoms with the bond length enlarged below it. Temperature dependence of dielectric constants displayed no sign, around 210 K, indicating the existence of (anti-)ferroelectricity. It was thus expected that the manner of off-center proton displacements along each hydrogen-bonded chain reveals a wave-like and incommensurate appearance below 210.4 K, referred to as the normal crystal lattice above it, and following locking to a wave-like but superlattice commensurate one at 159 K.
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DOI：
10.1002/cber.19731060412
发表时间：
1973
期刊：
影响因子：
--
作者：
D. Fenske;R. Mattes;J. Löns;Karl‐Friedrich Tebbe
通讯作者：
Karl‐Friedrich Tebbe
利用实数编码遗传算法根据玻璃态和晶态软有机材料的恒压热容数据确定声子态密度。
DOI：
10.1021/acs.jpcb.0c06666
发表时间：
2020
期刊：
The journal of physical chemistry. B
影响因子：
--
作者：
K. Ueda;Chie Morikawa;M. Oguni;Minami Kato;M. Tamura
通讯作者：
M. Tamura
通过实数编码遗传算法根据苯甲酸晶体的热容确定声子态密度的可靠性。
影响因子：
3.3
作者：
K. Ueda;M. Oguni
通讯作者：
M. Oguni
气相和链构象中次磷酸的结构、电位表面和振动光谱研究。
DOI：
10.5012/jkcs.2005.49.2.129
发表时间：
2005
期刊：
影响因子：
--
作者：
I. Ahmadi;H. Rahemi;S. Tayyari
通讯作者：
S. Tayyari
DOI：
10.1016/0022-2860(76)85092-2
发表时间：
1976
期刊：
影响因子：
--
作者：
S. Detoni;D. Hadzi;B. Orel
通讯作者：
B. Orel