Cunningham Ethan M, Green Alice E, Meizyte Gabriele, Gentleman Alexander S, Beardsmore Peter W, Schaller Sascha, Pollow Kai M, Saroukh Karim, Förstel Marko, Dopfer Otto, Schöllkopf Wieland, Fielicke André, Mackenzie Stuart R
Department of Chemistry, University of Oxford, Physical and Theoretical Chemistry Laboratory, South Parks Road, Oxford OX1 3QZ, UK.
Phys Chem Chem Phys. 2021 Jan 6;23(1):329-338. doi: 10.1039/d0cp05195k.
Understanding the catalytic decomposition of nitrous oxide on finely divided transition metals is an important environmental issue. In this study, we present the results of a combined infrared action spectroscopy and quantum chemical investigation of molecular N2O binding to isolated Aun+ (n ≤ 7) and Con+ (n ≤ 5) clusters. Infrared multiple-photon dissociation spectra have been recorded in the regions of both the N[double bond, length as m-dash]O (1000-1400 cm-1) and N[double bond, length as m-dash]N (2100-2450 cm-1) stretching modes of nitrous oxide. In the case of Aun+ clusters only the ground electronic state plays a role, while the involvement of energetically low-lying excited states in binding to the Con+ clusters cannot be ruled out. There is a clear preference for N-binding to clusters of both metals but some O-bound isomers are observed in the case of smaller Con(N2O)+ clusters.
了解一氧化二氮在细分过渡金属上的催化分解是一个重要的环境问题。在本研究中,我们展示了结合红外作用光谱和量子化学研究分子N₂O与孤立的Aun⁺(n ≤ 7)和Con⁺(n ≤ 5)团簇结合的结果。已在一氧化二氮的N=O(1000 - 1400 cm⁻¹)和N=N(2100 - 2450 cm⁻¹)伸缩模式区域记录了红外多光子解离光谱。对于Aun⁺团簇,只有基态起作用,而不能排除能量较低的激发态参与与Con⁺团簇的结合。两种金属的团簇都明显倾向于N键合,但在较小的Con(N₂O)⁺团簇中观察到一些O键合异构体。