Schwarzer Michael, Hertl Nils, Nitz Florian, Borodin Dmitriy, Fingerhut Jan, Kitsopoulos Theofanis N, Wodtke Alec M
Institute for Physical Chemistry, Georg-August University Goettingen, Tammannstraße 6, Goettingen 37077, Germany.
Department of Dynamics at Surfaces, Max Planck Institute for Multidisciplinary Sciences, Am Fassberg 11, Goettingen 37077, Germany.
J Phys Chem C Nanomater Interfaces. 2022 Sep 1;126(34):14500-14508. doi: 10.1021/acs.jpcc.2c04567. Epub 2022 Aug 19.
Thermal recombinative desorption rates of HD on Pd(111) and Pd(332) are reported from transient kinetic experiments performed between 523 and 1023 K. A detailed kinetic model accurately describes the competition between recombination of surface-adsorbed hydrogen and deuterium atoms and their diffusion into the bulk. By fitting the model to observed rates, we derive the dissociative adsorption energies ( = 0.98 eV; = 1.00 eV; = 0.99 eV) as well as the classical dissociative binding energy ϵ = 1.02 ± 0.03 eV, which provides a benchmark for electronic structure theory. In a similar way, we obtain the classical energy required to move an H or D atom from the surface to the bulk (ϵ = 0.46 ± 0.01 eV) and the isotope specific energies, = 0.41 eV and = 0.43 eV. Detailed insights into the process of transient bulk diffusion are obtained from kinetic Monte Carlo simulations.
通过在523至1023 K之间进行的瞬态动力学实验，报告了HD在Pd(111)和Pd(332)上的热复合脱附速率。一个详细的动力学模型准确地描述了表面吸附的氢原子和氘原子的复合与其向体相扩散之间的竞争。通过将模型与观测速率进行拟合，我们得出了离解吸附能（ = 0.98 eV； = 1.00 eV； = 0.99 eV）以及经典离解结合能ϵ = 1.02 ± 0.03 eV，这为电子结构理论提供了一个基准。以类似的方式，我们获得了将一个H或D原子从表面移动到体相所需的经典能量（ϵ = 0.46 ± 0.01 eV）以及同位素特定能量， = 0.41 eV和 = 0.43 eV。通过动力学蒙特卡罗模拟获得了对瞬态体相扩散过程的详细见解。
