Department of Physics, Federal University of Pelotas, P.O. Box 354, 96010-900 Pelotas, RS, Brazil.
Department of Science and Technology, Federal University of São Paulo, 12231-280 São José dos Campos, SP, Brazil.
J Chem Inf Model. 2021 May 24;61(5):2294-2301. doi: 10.1021/acs.jcim.1c00097. Epub 2021 May 3.
Our atomistic understanding of the physical-chemical parameters that drives the changes in the relative stability of clusters induced by adsorbed molecules is far from satisfactory. In this work, we employed density functional theory calculations to address this problem using CO adsorption on 13-atom transition-metal clusters, TM, namely, CO/TM, where TM = Ru, Rh, Pd, and Ag, and = 1-6. Unexpectedly, changes in the relative stability take place for all systems at a lower coverage, namely, at = 3 (Ru), 4 (Rh, Ag), and 2 (Pd). To address the effects that lead to changes in the stability, we proposed an energy decomposition scheme for the binding energy of the CO/TM systems, which yields that the change in relative stability is dominated by the interaction energy and cluster distortion energy upon adsorption, where the interaction energy is higher for high-energy unprotected clusters. Furthermore, we characterized all adsorption parameters, which helps us to complement our atomistic understanding.
我们对物理化学参数的原子级理解，这些参数驱动着被吸附分子引起的团簇相对稳定性的变化，远不能令人满意。在这项工作中，我们使用密度泛函理论计算来解决这个问题，使用 CO 在 13 个原子的过渡金属团簇 TM 上的吸附，即 CO/TM，其中 TM = Ru、Rh、Pd 和 Ag，并且 = 1-6。出乎意料的是，所有系统在较低的覆盖度下，即 = 3（Ru）、4（Rh、Ag）和 2（Pd）时，相对稳定性发生了变化。为了解释导致稳定性变化的影响，我们提出了 CO/TM 系统结合能的能量分解方案，该方案表明，相对稳定性的变化主要由吸附时的相互作用能和团簇变形能决定，其中高能无保护团簇的相互作用能更高。此外，我们还对所有的吸附参数进行了特征化，这有助于我们补充原子级的理解。
