Density Functional Theory Analysis for Orbital Interaction between Hypophosphite Ions and Metal Surfaces
Density Functional Theory Analysis for Orbital Interaction between Hypophosphite Ions and Metal Surfaces
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DOI：
10.1149/1.3623782
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发表时间：
2011-10
影响因子：
3.9
通讯作者：
Masahiro Kunimoto;H. Nakai;T. Homma
中科院分区：
文献类型：
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作者：
Masahiro Kunimoto;H. Nakai;T. Homma
为了阐明次磷酸根离子作为还原剂在不同金属表面（如Pd和Cu）上化学沉积的反应活性差异，采用密度泛函理论（DFT）对次磷酸根离子在这些表面上氧化活化态的电子结构进行了深入分析.在计算中，我们重点考虑了基元反应中的脱氢反应，它应该是基元反应步骤中的一个速率控制步骤。计算结果表明，次磷酸根离子与金属表面之间存在一种特殊的轨道相互作用。在Pd（111）上，次磷酸根离子中H的s轨道单独与Pd（111）的d或p轨道相互作用。这种相互作用诱导次磷酸根离子中H和P之间的反键相互作用，这是P-H裂解的原因。另一方面，在Cu（111）上，次磷酸根离子中H的s轨道和P的s轨道同时与Cu（111）的p轨道相互作用。这种相互作用几乎不引起次磷酸根离子中H和P之间的反键相互作用。这种轨道相互作用结构的差异可能与P-H断裂活性和次磷酸根离子在不同金属表面上的反应活性差异有关。
In order to elucidate the reactivity difference of hypophosphite ions used as reducing agents for electroless deposition on different metal surfaces, such as Pd and Cu, electronic structures of the activation states of hypophosphite ion oxidation on these surfaces were intensively analyzed by using Density Functional Theory (DFT). In the calculation, we focused on the dehydrogenation reaction which should be a rate-determining step in the elementary reaction steps. From the calculation results, a particular orbital interaction between the hypophosphite ion and the metal surface was observed. On Pd (111), the s-orbital of H in the hypophosphite ion interacts singly with the d-or p-orbital of Pd (111). This interaction induces an anti-bonding interaction between H and P in the hypophosphite ion, which is responsible for P–H cleavage. On the other hand, on Cu (111), the s-orbital of H and the s-orbital of P in a hypophosphite ion interact simultaneously with the p-orbital of Cu (111). This interaction barely induces an anti-bonding interaction between H and P in the hypophosphite ion. Such a difference in orbital interaction structures should be related to P–H cleavage activity and the reactivity difference of hypophosphite ion on each metal surface.