Bergeron Denis E, Musgrave Adam, Ayles Victoria L, Gammon Robert T, Silber James A E, Wright Timothy G
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, United Kingdom.
J Chem Phys. 2006 Oct 14;125(14):144319. doi: 10.1063/1.2348873.
We have employed (2 + 1) resonance enhanced multiphoton ionization spectroscopy to investigate the 3d and 4s Rydberg states of the NO molecule when bound to the surface of Rg(x) clusters (Rg = rare gas). We observe that the spectra of the NO-Ar(x) species converge in appearance as x increases, and this is discussed in terms of two Rg atoms interacting with the NO+ core, with other Rg atoms being "outside" the Rydberg orbital. We show that the interaction of each of the Rg atoms with the NO is essentially independent for the NO-Rg2 complexes: both by comparing our spectra for Rydberg states of NO-Rg and NO-Rg2, and from the results of ab initio calculations on NO+ - Rg and NO+ - Rg2. In addition, we discuss the disappearance of some electronic bands upon complexation in terms of Franck-Condon factors that are very sensitive to the angular coordinate. We relate our results to those of the bulk by comparing to the previously reported electronic spectroscopy of NO in both Rg matrices and He nanodroplets.
我们采用（2 + 1）共振增强多光子电离光谱法来研究与Rg(x)团簇（Rg = 稀有气体）表面结合时NO分子的3d和4s里德堡态。我们观察到，随着x的增加，NO-Ar(x)物种的光谱在外观上趋于收敛，这是从两个与NO⁺核心相互作用的Rg原子的角度进行讨论的，其他Rg原子处于里德堡轨道“外部”。我们表明，对于NO-Rg₂配合物，每个Rg原子与NO的相互作用基本独立：通过比较我们对NO-Rg和NO-Rg₂里德堡态的光谱，以及对NO⁺ - Rg和NO⁺ - Rg₂的从头算结果来证明。此外，我们根据对角坐标非常敏感的弗兰克 - 康登因子，讨论了络合时一些电子能带的消失情况。通过与先前报道的NO在Rg基质和He纳米液滴中的电子光谱进行比较，我们将我们的结果与体相结果联系起来。
