Jones Brant M, Hu Hang, Alexsandrov Alexandr, Smith William, Clark Aurora E, Li Xiaosong, Orlando Thomas M
Department of Chemistry, University of Washington, Seattle, Washington 98195, United States.
Department of Chemistry, Washington State University, Pullman, Washington 99164, United States.
J Phys Chem Lett. 2020 Dec 3;11(23):10088-10093. doi: 10.1021/acs.jpclett.0c02911. Epub 2020 Nov 12.
X-ray, energetic photon, and electron irradiation can ionize and electronically excite target atoms and molecules. These excitations undergo complicated relaxation and energy-transfer processes that ultimately determine the manifold system responses to the deposited excess energy. In weakly bound gas- and solution-phase samples, intermolecular Coulomb decay (ICD) and electron-transfer-mediated decay (ETMD) can occur with neighboring atoms or molecules, leading to efficient transfer of the excess energy to the surroundings. In ionic solids such as metal oxides, intra- and interatomic Auger decay produces localized final states that lead to lattice damage and typically the removal of cations from the substrate. The relative importance of Auger-stimulated damage (ASD) versus ICD and ETMD in microsolvated nanoparticle interfaces is not known. Though ASD is generally expected, essentially no lattice damage resulting from the ionization and electronic excitation of microsolvated boehmite (AlOOH) nanoplatelets has been detected. Rather efficient energy transfer and soft ionization of interfacial water molecules has been observed. This is likely a general phenomenon at gas-oxyhydroxide nanoparticle interfaces where the density of states of the ionized chemisorbed species significantly overlaps with the core hole states of the solid.
X射线、高能光子和电子辐照可使靶原子和分子发生电离并产生电子激发。这些激发过程会经历复杂的弛豫和能量转移过程,最终决定体系对沉积的多余能量的多种响应。在弱束缚的气相和溶液相样品中,分子间库仑衰变(ICD)和电子转移介导的衰变(ETMD)可与相邻原子或分子发生,导致多余能量有效地转移到周围环境中。在离子固体(如金属氧化物)中,原子内和原子间的俄歇衰变会产生局部终态,导致晶格损伤,通常还会使阳离子从基质中去除。在微溶剂化纳米颗粒界面中,俄歇激发损伤(ASD)与ICD和ETMD的相对重要性尚不清楚。尽管通常预期会发生ASD,但尚未检测到微溶剂化勃姆石(AlOOH)纳米片电离和电子激发导致的晶格损伤。相反,已观察到界面水分子的相当有效的能量转移和软电离。这可能是气体-羟基氧化物纳米颗粒界面处的普遍现象,其中电离化学吸附物种的态密度与固体的芯孔态有显著重叠。