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Pressure and Temperature Transformations of the Molecular Conformation and Crystal Structure of Ferrocene Fe2+(η5-C5H5)2–
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2022-02-09 , DOI: 10.1021/acs.jpcc.1c10063 Alexey V. Kuzmin 1 , Konstantin P. Meletov 1 , Maxim A. Faraonov 2
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2022-02-09 , DOI: 10.1021/acs.jpcc.1c10063 Alexey V. Kuzmin 1 , Konstantin P. Meletov 1 , Maxim A. Faraonov 2
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X-ray diffraction, optical spectroscopy, and numerical calculations were carried out on pristine ferrocene Fe2+(η5-C5H5)2– single crystals under various pressure/temperature conditions. Structural data were obtained at room temperature and pressures up to 6.5 GPa as well as at ambient pressure and low temperatures up to 100 K. The iron–carbon bond length (l = 2.043 Å under ambient conditions) shows linear temperature dependence and quadratic pressure dependence with the coefficients ∂l/∂T = −2.84 × 10–5 Å K–1, ∂l/∂P = −1.36 × 10–3 Å GPa–1, and ∂2l/∂P2 = −3.04 × 10–4 Å GPa–2, respectively. Jumping of the Fc molecular configuration between D5h and D5d conformations decreases at high pressure/low temperature, leading to complete ordering in low-temperature (LT, <161.3 K) and high-pressure (HP, >3 GPa) phases. The initially large bandwidth of lattice phonon modes increases with pressure to a maximum at 2 GPa and decreases to the common value after molecular ordering at pressures P > 3 GPa. The electronic structure calculations in the HP phase at high pressure show a linear increase in the fundamental gap Eg with the pressure coefficient of 28 meV/GPa. Optical transmission measurements at high pressure demonstrate an almost 2 times smaller pressure coefficient of about 12 meV/GPa and an abrupt decrease in the gap by ∼14.5 meV at P = 2 GPa.
中文翻译：
二茂铁Fe2+(η5-C5H5)2分子构象和晶体结构的压力和温度转换–
在各种压力/温度条件下，对原始二茂铁 Fe 2+ (η 5 -C 5 H 5 ) 2 -单晶进行了 X 射线衍射、光谱和数值计算。结构数据是在室温和最高 6.5 GPa 的压力以及环境压力和最高 100 K 的低温下获得的。铁碳键长（在环境条件下l = 2.043 Å）显示出线性温度依赖性和二次压力依赖性系数 ∂ l /∂ T = −2.84 × 10 –5 Å K –1 , ∂ l /∂ P= -1.36 × 10 –3 Å GPa –1和 ∂ 2 l /∂ P 2 = -3.04 × 10 –4 Å GPa –2。D 5 h和D 5 d构象之间 Fc 分子构型的跳跃在高压/低温下减少，导致在低温 (LT, <161.3 K) 和高压 (HP, >3 GPa) 阶段完全有序. 晶格声子模式的初始大带宽随着压力增加，在 2 GPa 处达到最大值，并在压力P下分子排序后减小到共同值> 3 帕。高压下 HP 相中的电子结构计算表明，基本间隙E g线性增加，压力系数为 28 meV/GPa。在高压下的光传输测量表明压力系数几乎小 2 倍，约为 12 meV/GPa，并且在P = 2 GPa 时间隙突然减小了 14.5 meV。
更新日期：2022-02-09
中文翻译：
二茂铁Fe2+(η5-C5H5)2分子构象和晶体结构的压力和温度转换–
在各种压力/温度条件下，对原始二茂铁 Fe 2+ (η 5 -C 5 H 5 ) 2 -单晶进行了 X 射线衍射、光谱和数值计算。结构数据是在室温和最高 6.5 GPa 的压力以及环境压力和最高 100 K 的低温下获得的。铁碳键长（在环境条件下l = 2.043 Å）显示出线性温度依赖性和二次压力依赖性系数 ∂ l /∂ T = −2.84 × 10 –5 Å K –1 , ∂ l /∂ P= -1.36 × 10 –3 Å GPa –1和 ∂ 2 l /∂ P 2 = -3.04 × 10 –4 Å GPa –2。D 5 h和D 5 d构象之间 Fc 分子构型的跳跃在高压/低温下减少，导致在低温 (LT, <161.3 K) 和高压 (HP, >3 GPa) 阶段完全有序. 晶格声子模式的初始大带宽随着压力增加，在 2 GPa 处达到最大值，并在压力P下分子排序后减小到共同值> 3 帕。高压下 HP 相中的电子结构计算表明，基本间隙E g线性增加，压力系数为 28 meV/GPa。在高压下的光传输测量表明压力系数几乎小 2 倍，约为 12 meV/GPa，并且在P = 2 GPa 时间隙突然减小了 14.5 meV。
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