Thorium fluorides ThF, ThF2, ThF3, ThF4, ThF3(F2), and ThF5- characterized by infrared spectra in solid argon and electronic structure and vibrational frequency calculations.
Thorium fluorides ThF, ThF2, ThF3, ThF4, ThF3(F2), and ThF5- characterized by infrared spectra in solid argon and electronic structure and vibrational frequency calculations.
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DOI：
10.1021/ic401107w
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发表时间：
2013-06
影响因子：
4.6
通讯作者：
L. Andrews;K. S. Thanthiriwatte;Xuefeng Wang;D. Dixon
中科院分区：
文献类型：
--
作者：
L. Andrews;K. S. Thanthiriwatte;Xuefeng Wang;D. Dixon
激光烧蚀的Th原子与F2的反应产生作为主要产物的ThF 4，这基于与在800-850 °C下从固体的蒸气记录的矩阵光谱的一致性。较弱的高频带（567.2、564.8），（575.9，575.1），以及（531.0，528.4）cm（-1）在氩气中的位置被指定为ThF，ThF 2和ThF 3，ThF 3（F2）基于它们在增加试剂浓度、退火和辐照时的化学行为，使用NF 3，OF 2和HF作为F原子源，并与在DFT/B3 LYP和CCSD（T）水平上计算的频率进行了比较，其中在Th上设置了大分段+ ECP基组，在F上设置了aug-cc-pVTZ基组。在460 cm（-1）处的另一个较宽的谱带被指定为ThF 5（-）阴离子。三角双锥ThF 5（-）阴离子（计算的电子脱离能为7.17 eV）在全汞弧照射下以ThF 3（F2）和F3（-）为代价增加。计算表明[ThF 3（+）][F2（-）]是一种具有侧键F2（-）亚基的离子复合物。本文报道了新的五配位钍物种的第一个证据，包括独特的[ThF_3（+）][F_2（-）]离子自由基-离子对分子及其电子捕获产物，非常稳定的ThF_5（-）阴离子。
Reactions of laser-ablated Th atoms with F2 produce ThF4 as the major product based on agreement with matrix spectra recorded of the vapor from the solid at 800-850 °C. Weaker higher-frequency bands at (567.2, 564.8), (575.9, 575.1), and (531.0, 528.4) cm(-1) in argon are assigned to ThF, ThF2 and ThF3, ThF3(F2) on the basis of their chemical behavior upon increasing reagent concentrations, annealing, and irradiation, the use of NF3, OF2, and HF as F-atom sources, and a comparison with frequencies calculated at the DFT/B3LYP and CCSD(T) levels with a large segmented + ECP basis set on Th and the aug-cc-pVTZ basis set on F. An additional broader band at 460 cm(-1) is assigned to the ThF5(-) anion. The trigonal-bipyramidal ThF5(-) anion (calculated electron detachment energy of 7.17 eV) increases at the expense of ThF3(F2) and F3(-) on full mercury arc irradiation. [ThF3(+)][F2(-)] is shown by calculations to be an ionic complex with a side-bound F2(-) subunit. This paper reports the first evidence for novel pentacoordinated thorium species including the unique [ThF3(+)][F2(-)] ionic radical-ion pair molecule and its electron-capture product, the very stable ThF5(-) anion.