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The rotational spectrum and structure for the argon-cyclopentadienyl thallium van der Waals complex: Experimental and computational studies of noncovalent bonding in an organometallic -complex
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10.1063/1.2955739
/content/aip/journal/jcp/129/5/10.1063/1.2955739
http://aip.metastore.ingenta.com/content/aip/journal/jcp/129/5/10.1063/1.2955739

Figures

Image of FIG. 1.
FIG. 1.

The basic structure of the argon-cyclopentadienyl thallium dimer in the principal inertial axis system.

Image of FIG. 2.
FIG. 2.

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.

Image of FIG. 3.
FIG. 3.

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).

Image of FIG. 4.
FIG. 4.

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 .

Image of FIG. 5.
FIG. 5.

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.

Image of FIG. 6.
FIG. 6.

Zigzag structure of the chain, as reported for the x-ray structure (Refs. 9 and 10).

Image of FIG. 7.
FIG. 7.

Example spectrum for the (a), (b), and (c) transitions.

Tables

Generic image for table
Table I.

The results of geometry optimizations using the MP2 method with a small-core pseudopotential cc-pVDZ-PP basis sets for the thallium atom.

Generic image for table
Table II.

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 .

Generic image for table
Table III.

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.

Generic image for table
Table IV.

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.

Generic image for table
Table V.

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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/content/aip/journal/jcp/129/5/10.1063/1.2955739
2008-08-04
2014-04-24
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Scitation: The rotational spectrum and structure for the argon-cyclopentadienyl thallium van der Waals complex: Experimental and computational studies of noncovalent bonding in an organometallic π-complex
http://aip.metastore.ingenta.com/content/aip/journal/jcp/129/5/10.1063/1.2955739
10.1063/1.2955739
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