Insight from first principles into the nature of the bonding between water molecules and 4d metal surfaces
Insight from first principles into the nature of the bonding between water molecules and 4d metal surfaces
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DOI：
10.1063/1.3125002
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发表时间：
2009-05-14
影响因子：
4.4
通讯作者：
Scheffler, Matthias
中科院分区：
文献类型：
--
作者：
Carrasco, Javier;Michaelides, Angelos;Scheffler, Matthias
我们通过对H2O单体在一系列紧密堆积的过渡金属表面：Ru(0001)，Rh(111)，Pd(111)和Ag(111)上的吸附的密度泛函理论(DFT)研究了水分子与金属表面之间的键的性质。为了了解4d系列能量和结构趋势背后的原因，我们使用了一系列分析工具，如电子反应性函数、态密度的分解、电子密度差和对单个Kohn-Sham轨道的检查。从我们的密度泛函计算得到的结果使我们能够合理地将水和过渡金属表面之间的键合为共价和静电相互作用的平衡。基于H2O分子轨道之间的所谓双中心四电子相互作用的前线轨道方案-主要是表面的1b(1)-和d-带态-被证明对理解这些系统具有深刻的意义。
We address the nature of the bond between water molecules and metal surfaces through a systematic density-functional theory (DFT) study of H2O monomer adsorption on a series of close-packed transition metal surfaces: Ru(0001), Rh(111), Pd(111), and Ag(111). Aiming to understand the origin behind energetic and structural trends along the 4d series we employ a range of analysis tools such as the electron reactivity function, decomposition of densities of states, electron density differences, and inspection of individual Kohn-Sham orbitals. The results obtained from our DFT calculations allow us to rationalize the bonding between water and transition metal surfaces as a balance of covalent and electrostatic interactions. A frontier orbital scheme based on so-called two-center four-electron interactions between the molecular orbitals of H2O-mainly the 1b(1)- and d-band states of the surface proves incisive in understanding these systems.