The basic structure of the argon-cyclopentadienyl thallium dimer in the principal inertial axis system.
The structure of argon-cyclopentadienyl thallium dimer in the -coordinate system with origin at the Cp centroid, showing structural parameters , , and used in structural analysis and calculations. The measured vdW distance from argon to centroid(x) in the Cp ring is . The experimental angle measuring from argon to centroid to thallium is , corresponding to . is the azimuthal angle for rotation of the Ar atom around the -axis.
Plot of the binding energy as a function of for MP2 and DFT calculations. denotes counterpoise corrected energy. The geometry of CpTl was fixed to the microwave structure (Ref. 39).
A potential energy surface profile for Ar–Cp–Tl evaluated at the MP2/aug-cc-pVTZ-PP (thallium)/aug-cc-pVTZ(Ar, C, H). The calculated MP2 binding energy for the lowest energy structure is about .
The optimized geometries for the and chain subunits. Calculations for structures I and II converged with real vibration frequencies. Structures III and IV are transition states and likely do not represent stable structures.
Zigzag structure of the chain, as reported for the x-ray structure (Refs. 9 and 10).
Example spectrum for the (a), (b), and (c) transitions.
The results of geometry optimizations using the MP2 method with a small-core pseudopotential cc-pVDZ-PP basis sets for the thallium atom.
Summary of argon-cyclopentadienyl thallium BSSE-corrected binding energies evaluated for the microwave measured structure at the separation distance . The ZPVE correction at the MP2/aug-cc-pVDZ-PP/ aug-cc-pVDZ level of calculation is .
Measured rotational transition frequency and fit residual (measured frequency—calculated frequency) for the argon-cyclopentadienyl thallium dimer. Measured frequency and residual of errors values are in MHz.
Measured rotational and centrifugal distortion constants obtained from the fit shown in TABLE III for argon-cyclopentadienyl thallium dimer. The rotational constant is fixed to the MP2 value. The standard error is . (fit) denotes the standard deviation of the fit.
Experimental parameters for the Ar–Cp–Tl, Ar-benzene, and Ar-furan complexes. is the approximate binding energy calculated using the pseudodiatomic model with Lennard-Jones potential.
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