Krüger Bastian C, Meyer Sven, Kandratsenka Alexander, Wodtke Alec M, Schäfer Tim
Institute of Physical Chemistry, Georg-August University of Göttingen , Tammannstraße 6, 37077 Göttingen, Germany.
Department of Dynamics at Surfaces, Max Planck Institute for Biophysical Chemistry , Am Faßberg 11, 37077 Göttingen, Germany.
J Phys Chem Lett. 2016 Feb 4;7(3):441-6. doi: 10.1021/acs.jpclett.5b02448. Epub 2016 Jan 19.
Multiquantum relaxation of highly vibrationally excited nitric oxide on noble metals has become one of the best studied examples of the Born-Oppenheimer approximation's failure to describe molecular interactions at metal surfaces. When first reported, relaxation of highly vibrationally excited NO occurring in collisions with Au(111) surfaces exhibited the largest vibrational inelasticity seen in molecule-surface collisions, and no system has been found to date exhibiting a greater vibrational inelasticity. In this work, we compare the relaxation of NO(v = 11) in scattering events on Ag(111) to that on Au(111). The relaxation probability and the average vibrational energy loss are much higher when scattering from Ag(111). We discuss possible reasons for this remarkable phenomenon, which may be related to the dissociation of NO, possible on Ag(111) at lower energy compared with Au(111).
高振动态激发的一氧化氮在贵金属上的多量子弛豫已成为研究得最为透彻的例子之一，用以说明玻恩-奥本海默近似在描述分子与金属表面相互作用时的失效情况。首次报道时，高振动态激发的一氧化氮与金（111）表面碰撞时发生的弛豫表现出分子-表面碰撞中最大的振动非弹性，并且迄今为止尚未发现有其他体系表现出更大的振动非弹性。在这项工作中，我们将一氧化氮（v = 11）在银（111）表面散射事件中的弛豫与在金（111）表面的弛豫进行了比较。当从银（111）表面散射时，弛豫概率和平均振动能量损失要高得多。我们讨论了这一显著现象的可能原因，这可能与一氧化氮的解离有关，相比于金（111），银（111）在较低能量下可能发生一氧化氮的解离。
