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Reactions of early lanthanide metal atoms (Nd, Sm, Eu) with water molecules. A matrix isolation infrared spectroscopic and theoretical study

机译:早期镧系金属原子(Nd,Sm,Eu)与水分子的反应。矩阵隔离红外光谱法及理论研究

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摘要

The reactions of early lanthanide metal atoms Nd, Sm, and Eu with water molecules have been investigated using matrix isolation infrared spectroscopy and density functional calculations. The reaction intermediates and products were identified on the basis of isotopic labeled experiments and density functional frequency calculations. The ground state metal atoms react with water to form the M(H2O) and M(H2O)(2) complexes spontaneously on annealing (M = Nd, Sm, Eu). The M(H2O) complexes isomerize to the inserted HMOH molecules under red light irradiation, which further decompose to give the metal monoxides upon UV light irradiation. The Nd(H2O)(2) complex decomposes to form the trivalent HNd(OH)(2) molecule, while the Sm(H2O)(2) and Eu(H2O)(2) complexes rearrange to the divalent Sm(OH)(2) and Eu(OH)(2) molecules under red light irradiation.
机译:早期镧系金属原子Nd,Sm和Eu与水分子的反应已通过基质隔离红外光谱和密度泛函计算进行了研究。反应中间体和产物是根据同位素标记的实验和密度函数频率计算确定的。基态金属原子与水反应,在退火时自发形成M(H2O)和M(H2O)(2)络合物(M = Nd,Sm,Eu)。 M(H2O)配合物在红光照射下异构化为插入的HMOH分子,在紫外光照射下进一步分解为金属一氧化物。 Nd(H2O)(2)配合物分解形成三价HNd(OH)(2)分子,而Sm(H2O)(2)和Eu(H2O)(2)配合物重新排列为二价Sm(OH)( 2)和Eu(OH)(2)分子在红光照射下。

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