Clusters containing open-shell molecules. III. Quantum five-dimensional/two-surface bound-state calculations on ArnOH van der Waals clusters (X2Π, n=4 to 12)

Abstract

The full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. This paper presents a theoretical study of the bound states of the open-shell OH radical in its ground electronic state (X 2 ⌸) interacting with n Ar atoms, for n from 4 to 12. After freezing the geometry of the Ar n cage or subunit at the equilibrium structure ͑preceding paper͒, we carry out nonadiabatic five-dimensional quantum dynamics calculations on two coupled potential energy surfaces, using an extension of the method previously applied to closed-shell Ar n HF clusters ͓J. Chem. Phys. 103, 1829 ͑1995͔͒. The method is based on a discrete variable representation ͑DVR͒ for the translational motion of OH relative to Ar n , combined with a finite basis representation of the OH hindered rotation and electronic structure, including spin-orbit effects. The pattern of OH hindered rotor levels in clusters is similar to that in Ar-OH itself, though extended over three to four times the energy range for nϭ4 to 9. Ar 12 OH has a nearly spherical shell of Ar atoms around the OH, so the anisotropic splitting is very small. For nϭ10 and 11, the anisotropy may be viewed as arising from holes in an otherwise spherical shell, and the resulting patterns of hindered rotor levels are inverted versions of those for Ar 2 OH and Ar-OH.

Anomalous Λ-Doubling in the Infrared Spectrum of the Hydroxyl Radical in Helium Nanodroplets

“…This difference potential couples states that differ by 2λ, which leads to parity splitting of rotational levels in the complex. However, this difference potential operator actually vanishes in He droplets due to the local 2-fold symmetry about the OH molecular axis, an effect discussed extensively for XH–(Ar) n (X = C or O) clusters. − …”

Clusters containing open-shell molecules. II. Equilibrium structures of ArnOH Van der Waals clusters (X2Π, n=1 to 15)

“…In a companion article, 38 we will use the structures determined here to carry out five-dimensional/two-surface ͑5D/ FIG. 13.…”

“…We then add the Ar-Ar contribution ͑7͒ and use the lower of the two resulting surfaces to find the structure of the global minimum and low-lying structural isomers. In an accompanying paper, 38 we will investigate the dynamics of Ar n OH (X 2 ⌸) clusters considering both surfaces and the coupling between them.…”

“…In the present work, this will be extended to Ar n OH clusters, in order to find their global and local minimum structures. In a companion paper, 38 we will develop the theory needed to carry out the analog of quantum fivedimensional bound-state calculations on Ar n OH clusters, including both potential energy surfaces that correlate with OH (X 2 ⌸).…”

Optical Spectroscopy of Potassium-Doped Argon Clusters. Experiments and Quantum-Chemistry Calculations

“…Many spectroscopic experiments have been performed on doped rare-gas clusters; the results are reviewed in several monographs covering broader themes in cluster science. − Ongoing fields of experimental research utilizing Ar clusters are the investigation of the dynamics in chemical reactions, , as well as probing solvent−solute interactions by photodissociation of molecules in/on rare-gas clusters. , Theoretical aspects concerning solvationin particular nonadditive effects and open-shell dopantsare addressed by Bačić, Hutson, and co-workers, − prompted in part by recent experimental results of Nauta and Miller …”