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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Ammonia Activation by Early Transition Metal Atoms (Sc, Ti, and V). Matrix Isolation Infrared Spectroscopic and Density Functional Theory Studies
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Ammonia Activation by Early Transition Metal Atoms (Sc, Ti, and V). Matrix Isolation Infrared Spectroscopic and Density Functional Theory Studies

机译:早期过渡金属原子(Sc,Ti和V)激活氨气。基质隔离红外光谱和密度泛函理论研究

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摘要

Reactions of the early transition metal atoms Sc, T, and V with NH_3 molecules in solid argon matrix have been studied by infrared spectroscopy and density functional calculations. It is found that the ground-state metal atoms reacted with NH_3 to form the MNH_3 (M = Sc, Ti, and V) complexes spontaneously on annealing. The MNH_3 complexes underwent photochemical rearrangement to the HMNH_2 molecules. The HScNH_2 molecule further decomposed to ScNH + H_2 upon ultraviolet-visible irradiation. While in the Ti + NH_3 and V + NH_3 reaction systems, the novel H_2TiNH and H_2VNH species were the ultimate products generated from the photoinduced isomerization of the HTiNH_2 and HVNH_2 intermediates. All the reaction intermediates and products have been identified by isotopic substitutions and by density functional theoretical frequency calculations. qualitative analysis of the possible reaction paths for these reactions is given, including various minima and transition states. The results have been compared with previous works covering middle transition metal atoms as well as main group atom reactions with NH_3 to obtain periodic trends for these reactions.
机译:通过红外光谱和密度泛函计算研究了早期过渡金属原子Sc,T和V与固体氩基体中NH_3分子的反应。发现基态金属原子在退火时自发形成NH_3(M = Sc,Ti和V)配合物。 MNH_3配合物进行了光化学重排为HMNH_2分子。 HScNH_2分子在紫外可见光照射下进一步分解为ScNH + H_2。在Ti + NH_3和V + NH_3反应体系中,新型H_2TiNH和H_2VNH物种是HTiNH_2和HVNH_2中间体的光致异构化生成的最终产物。所有反应中间体和产物均已通过同位素取代和密度泛函理论频率计算确定。给出了这些反应可能的反应路径的定性分析,包括各种最小和过渡态。将结果与先前的研究进行了比较,该研究涉及中间过渡金属原子以及与NH_3的主族原子反应,以获得这些反应的周期性趋势。

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