Tsyshevsky Roman V, Zverev Anton, Mitrofanov Anatoly, Rashkeev Sergey N, Kuklja Maija M
Department of Materials Science and Engineering, University of Maryland, College Park, MD 20742, USA.
Department of Organic and Physical Chemistry, Kemerovo State University, Kemerovo 650043, Russia.
Molecules. 2016 Feb 29;21(3):289. doi: 10.3390/molecules21030289.
Optical absorption measurements are combined with electronic structure calculations to explore photochemistry of an α-Al₂O₃-PETN interface formed by a nitroester (pentaerythritol tetranitrate, PETN, C₅H₈N₄O12) and a wide band gap aluminum oxide (α-Al₂O₃) substrate. The first principles modeling is used to deconstruct and interpret the α-Al₂O₃-PETN absorption spectrum that has distinct peaks attributed to surface F⁰-centers and surface-PETN transitions. We predict the low energy α-Al₂O₃ F⁰-center-PETN transition, producing the excited triplet state, and α-Al₂O₃ F⁰-center-PETN charge transfer, generating the PETN anion radical. This implies that irradiation by commonly used lasers can easily initiate photodecomposition of both excited and charged PETN at the interface. The feasible mechanism of the photodecomposition is proposed.
光学吸收测量与电子结构计算相结合，以探究由硝酸酯（季戊四醇四硝酸酯，PETN，C₅H₈N₄O₁₂）和宽带隙氧化铝（α-Al₂O₃）衬底形成的α-Al₂O₃-PETN界面的光化学。第一性原理建模用于解构和解释α-Al₂O₃-PETN吸收光谱，该光谱具有归因于表面F⁰中心和表面-PETN跃迁的明显峰。我们预测了产生激发三重态的低能量α-Al₂O₃ F⁰中心-PETN跃迁，以及产生PETN阴离子自由基的α-Al₂O₃ F⁰中心-PETN电荷转移。这意味着常用激光照射可轻易引发界面处激发态和带电PETN的光分解。提出了光分解的可行机制。
