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Properties of Lanthanide Hydroxide Molecules Produced in Reactions of Lanthanide Atoms with H2O2 and H2 + O2 Mixtures: Roles of the +I, +II, +III, and +IV Oxidation States
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-02-20 00:00:00 , DOI: 10.1021/acs.jpca.6b12607
Xuefeng Wang 1, 2 , Lester Andrews 1 , Zongtang Fang 3 , K. Sahan Thanthiriwatte 3 , Mingyang Chen 3 , David A. Dixon 3
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2017-02-20 00:00:00 , DOI: 10.1021/acs.jpca.6b12607
Xuefeng Wang 1, 2 , Lester Andrews 1 , Zongtang Fang 3 , K. Sahan Thanthiriwatte 3 , Mingyang Chen 3 , David A. Dixon 3
Affiliation
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The reactions of laser-ablated lanthanide metal atoms with hydrogen peroxide or hydrogen plus oxygen mixtures have been studied experimentally in a solid argon matrix and theoretically with the ab initio MP2 and CCSD(T) methods. The Ln(OH)3 and Ln(OH)2 molecules and Ln(OH)2+ cations are the major products, and the reactions to form those hydroxides are predicted to be highly exothermic at the CCSD(T) level. Vibronic interactions are hypothesized to contribute to the abnormalities in deuterium shifts for Ln–OH(D) stretching modes for several hydroxides, consistent with CASSCF calculations. Additional new absorptions were assigned as HLnO or LnOH and OLnOH molecules. The tetrahydroxides of Ce, Pr, and Tb have also been observed. These reactive intermediates were identified from their matrix infrared spectra by using D2O2, HD, D2, 16,18O2, and 18O2 isotopic substitution, by matching observed frequencies with values calculated by electronic structure methods, and by following the trends observed in frequencies going through different lanthanide metal hydroxide series across the periodic table. The lanthanides are in the +II oxidation state for Ln(OH)2 and are in the +III oxidation state for Ln(OH)3 and Ln(OH)2+.
中文翻译：
镧系元素原子与H 2 O 2和H 2 + O 2混合物反应生成的氢氧化镧分子的性质：+ I，+ II，+ III和+ IV氧化态的作用
激光烧蚀的镧系金属原子与过氧化氢或氢加氧混合物的反应已在固体氩气基质中进行了实验研究，并从头开始采用MP2和CCSD（T）方法进行了理论研究。Ln（OH）3和Ln（OH）2分子以及Ln（OH）2 +阳离子是主要产物，形成这些氢氧化物的反应预计在CCSD（T）水平上会放热。假设振动相互作用会导致几种氢氧化物的Ln–OH（D）拉伸模式的氘位移异常，与CASSCF计算一致。额外的新吸收被指定为HLnO或LnOH和OLnOH分子。还观察到了Ce，Pr和Tb的四氢氧化物。这些活性中间体从它们的矩阵红外光谱通过使用d标识2 ö 2，HD，d 2，16,18 Ò 2，和18 ö 2通过将观测到的频率与通过电子结构方法计算出的值进行匹配，并遵循在整个元素周期表中经过不同镧系元素金属氢氧化物序列的频率中观察到的趋势，来进行同位素取代。镧系元素对Ln（OH）2呈+ II氧化态，对Ln（OH）3和Ln（OH）2 +呈+ III氧化态。
更新日期：2017-02-20
中文翻译：
镧系元素原子与H 2 O 2和H 2 + O 2混合物反应生成的氢氧化镧分子的性质：+ I，+ II，+ III和+ IV氧化态的作用
激光烧蚀的镧系金属原子与过氧化氢或氢加氧混合物的反应已在固体氩气基质中进行了实验研究，并从头开始采用MP2和CCSD（T）方法进行了理论研究。Ln（OH）3和Ln（OH）2分子以及Ln（OH）2 +阳离子是主要产物，形成这些氢氧化物的反应预计在CCSD（T）水平上会放热。假设振动相互作用会导致几种氢氧化物的Ln–OH（D）拉伸模式的氘位移异常，与CASSCF计算一致。额外的新吸收被指定为HLnO或LnOH和OLnOH分子。还观察到了Ce，Pr和Tb的四氢氧化物。这些活性中间体从它们的矩阵红外光谱通过使用d标识2 ö 2，HD，d 2，16,18 Ò 2，和18 ö 2通过将观测到的频率与通过电子结构方法计算出的值进行匹配，并遵循在整个元素周期表中经过不同镧系元素金属氢氧化物序列的频率中观察到的趋势，来进行同位素取代。镧系元素对Ln（OH）2呈+ II氧化态，对Ln（OH）3和Ln（OH）2 +呈+ III氧化态。
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