National Institute of Standards and Technology, 100 Bureau Drive, Gaithersburg, Maryland 20899, USA.
J Chem Phys. 2013 Sep 28;139(12):124310. doi: 10.1063/1.4821828.
The vapors in equilibrium with condensates of DyI3, DyI3/InI, TmI3, and TmI3/TlI were observed over the temperature range from 900 K to 1400 K using x-ray induced fluorescence. The total densities of each element (Dy, Tm, In, Tl, and I) in the vapor, summed over all atomic and molecular species, were determined. Dramatic enhancements in the total vapor densities of Dy and Tm were observed in the vapors over DyI3/InI and TmI3/TlI as compared to the vapors over pure DyI3 and pure TmI3, respectively. An enhancement factor exceeding 10 was observed for Dy at T ≈ 1020 K, decreasing to 0 at T ≈ 1250 K. An enhancement factor exceeding 20 was observed for Tm at T ≈ 1040 K, decreasing to 0 at T ≈ 1300 K. Such enhancements are expected from the formation of the vapor-phase hetero-complexes DyInI4 and TmTlI4. Numerical simulations of the thermo-chemical equilibrium suggest the importance of additional complexes in liquid phases. A description of the measurement technique is given. Improvements in the absolute calibration lead to an approximately 40% correction to previously reported preliminary results [J. J. Curry et al., Chem. Phys. Lett. 507, 52 (2011); Appl. Phys. Lett. 100, 083505 (2012)].
使用 X 射线诱导荧光，观察了 DyI3、DyI3/InI、TmI3 和 TmI3/TlI 的冷凝物平衡蒸气，温度范围从 900 K 到 1400 K。确定了蒸气中每种元素（Dy、Tm、In、Tl 和 I）的总密度，这些元素在所有原子和分子物种中进行了总和。与纯 DyI3 和纯 TmI3 相比，在 DyI3/InI 和 TmI3/TlI 上的蒸气中，Dy 和 Tm 的总蒸气密度明显增加。在 T ≈ 1020 K 时，Dy 的增强因子超过 10，在 T ≈ 1250 K 时降至 0。在 T ≈ 1040 K 时，Tm 的增强因子超过 20，在 T ≈ 1300 K 时降至 0。这些增强是由气相异质配合物 DyInI4 和 TmTlI4 的形成引起的。热化学平衡的数值模拟表明了液相中额外配合物的重要性。介绍了测量技术。绝对校准的改进导致对以前报道的初步结果进行了约 40%的修正[J. J. Curry 等人，Chem. Phys. Lett. 507, 52 (2011); Appl. Phys. Lett. 100, 083505 (2012)]。
