Reliability of the Phonon Density of States Determined by Real-Coded Genetic Algorithm from Heat Capacities of Benzoic Acid Crystals.
Reliability of the Phonon Density of States Determined by Real-Coded Genetic Algorithm from Heat Capacities of Benzoic Acid Crystals.
复制标题
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。
DOI：
10.1021/acs.jpcb.1c01722
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发表时间：
2021
影响因子：
3.3
通讯作者：
M. Oguni
中科院分区：
文献类型：
--
作者：
K. Ueda;M. Oguni
采用绝热量热法测定了结晶苯甲酸（BAh）及其氘化类似物（c6h5good, BAd）的恒压热容（CPs），并采用仅代沟+实编码系集交叉的实编码遗传算法（RCGA）从它们的CP数据中确定了态声子密度（g(ω)）。g（ω）的分布与分子振动模式的光谱观测值基本一致，表明RCGA测定的g（ω）具有足够的可靠性。基于CPs在30-130 K温度范围内表现出反同位素效应的事实，利用测定的g(ω)s来研究该效应的分子机制：BAd的g（ω）在ω = 80-100和150-230 K范围内表现出蓝移，即BAh的蓝移。从g（ω）和光谱结果的综合考虑表明，BA中O- h···O氢键与中间体相互作用之间存在反合作关系。
Constant-pressure heat capacities (CPs) of crystalline benzoic acid (BAh) and its deuterated analogue (C6H5COOD, BAd) were measured by adiabatic calorimetry, and the phonon density (g(ω)) of states was determined from their CP data using a real-coded genetic algorithm (RCGA) with just generation gap + real-coded ensemble cross-over. The distribution of g(ω) was in reasonable agreement with the spectroscopic one observed for molecular vibration modes, indicating sufficient reliability of g(ω) determined by the RCGA. Based on the fact that CPs reveals an inverse-isotope effect in the temperature range 30-130 K, the determined g(ω)s were used to investigate the molecular mechanism of the effect: g(ω) of BAd revealed blue shifts in the ranges of ω = 80-100 and 150-230 K, as referred to that of BAh. It was suggested from the combined considerations on g(ω) and spectroscopic results that an anticooperative correlation exists between O-H···O hydrogen bonds and interdimer interactions in BA.