Rubli Peter T, Haakansson Christian T, Pearcy Philip A J, Spratt Ruby G, Bakker Joost M, Watson Peter D, Mackenzie Stuart R
Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA U.K.
HFML-FELIX, Toernooiveld 7, Nijmegen 6525 ED, the Netherlands.
J Phys Chem A. 2025 Jul 3;129(26):5810-5819. doi: 10.1021/acs.jpca.5c02939. Epub 2025 Jun 24.
Nitric oxide binding to and/or dissociation on isolated cobalt cluster cations, Co ( = 3-14), has been investigated using a combination of infrared multiple photon dissociation spectroscopy and density functional theory. Rich vibrational structure in the 300-800 cm spectral region reflects predominantly dissociative adsorption, though a minor molecularly bound isomer cannot be ruled out. Inert messenger tagging reveals nitrogen and oxygen atoms bound in bridged and/or three-atom sites. The calculated potential energy surface associated with the reaction between NO and Co confirms only submerged barriers to dissociation and unusual full insertion of the N atom, which binds to all three metal atoms. The second NO adsorbed also dissociates on all clusters studied here, with the smallest cluster, [CoNO]-Ar, adopting an unusual planar cyclic structure with O atoms and an N molecule inserted between adjacent Co atoms.
利用红外多光子解离光谱和密度泛函理论相结合的方法,研究了一氧化氮在孤立钴簇阳离子Co(n = 3 - 14)上的吸附和/或解离情况。在300 - 800厘米光谱区域丰富的振动结构主要反映了解离吸附,不过也不能排除少量分子结合异构体的存在。惰性信使标记揭示了氮和氧原子结合在桥连和/或三原子位点。与NO和Co之间反应相关的计算势能面证实,只有解离的潜在势垒以及氮原子不寻常的完全插入,氮原子与所有三个金属原子结合。在此研究的所有簇上,吸附的第二个NO也会解离,最小的簇[CoNO]⁻Ar采用一种不寻常的平面环状结构,氧原子和一个氮分子插入相邻的钴原子之间。