Clabaut Paul, Staub Ruben, Galiana Joachim, Antonetti Elise, Steinmann Stephan N
Univ Lyon, Ecole Normale Supérieure de Lyon, CNRS Université Lyon 1, Laboratoire de Chimie UMR 5182, 46 allée d'Italie, F-69364 Lyon, France.
J Chem Phys. 2020 Aug 7;153(5):054703. doi: 10.1063/5.0013040.
Water molecules adsorbed on noble metal surfaces are of fundamental interest in surface science, in heterogeneous catalysis, and as a model for the metal/water interface. Herein, we analyze 28 water structures adsorbed on five noble metal surfaces (Cu, Ag, Au, Pd, and Pt) via density functional theory and energy decomposition analysis based on the block localized wave function technique. Structures, ranging from monomers to ice adlayers, reveal that the charge transfer from water to the surface is nearly independent from the charge transfer between the water molecules, while the polarization energies are cooperative. Dense water-water networks with small surface dipoles, such as the 39×39 unit cell [experimentally observed on Pt(111)], are favored compared to the highly ordered and popular H and H phases. The second main result of our study is that the many-body interactions, which stabilize the water assemblies on the metal surfaces, are dominated by the polarization energies, with the charge transfer scaling with the polarization energies. Hence, if an empirical model could be found that reproduces the polarization energies, the charge transfer could be predicted as well, opening exciting perspectives for force field development.
吸附在贵金属表面的水分子在表面科学、多相催化以及作为金属/水界面模型方面具有重要的基础研究意义。在此，我们基于块定域波函数技术，通过密度泛函理论和能量分解分析，研究了吸附在五种贵金属表面（铜、银、金、钯和铂）上的28种水结构。从单体到冰吸附层的结构表明，从水到表面的电荷转移几乎与水分子之间的电荷转移无关，而极化能是协同的。与高度有序且常见的H相和H相相比，具有小表面偶极子的密集水 - 水网络，如在Pt(111)上实验观察到的39×39晶胞，更受青睐。我们研究的第二个主要结果是，稳定金属表面水聚集体的多体相互作用主要由极化能主导，电荷转移与极化能成比例。因此，如果能找到一个能再现极化能的经验模型，那么电荷转移也可以被预测，这为力场发展开辟了令人兴奋的前景。
