^{1}, Larry A. Viehland

^{1}, Edmond P. F. Lee

^{2}, W. H. Breckenridge

^{3}, Carolyn D. Withers

^{4}, Adrian M. Gardner

^{4}, Richard J. Plowright

^{4}and Timothy G. Wright

^{4,a)}

### Abstract

We present high-level ab initio potential energy curves for barium cations and dications interacting with RG atoms . These potentials are employed to derive spectroscopic parameters for the and complexes, and also to derive the transport coefficients for and moving through a bath of the rare gas. The results are compared to the limited experimental data, which generally show reasonable agreement. We identify a large change in binding energy going from and to , which is not present in , and show that this is due to significant dispersion interactions in .

The authors are grateful to the EPSRC for the award of computer time at the Rutherford Appleton Laboratories under the auspices of the Computational Chemistry Working Party (CCWP), which enabled these calculations to be performed. The work of LAV and MFM was supported by the National Science Foundation under Grant No. CHE-0718024. The collaboration between T.G.W. and W.H.B. has been aided by travel grants from the Chemistry Department at the University of Utah, and the Royal Society (London).

I. INTRODUCTION

II. COMPUTATIONAL DETAILS

III. RESULTS

A. Spectroscopy

B. Transport properties

IV. DISCUSSION

V. CONCLUSIONS

### Key Topics

- Carrier mobility
- 23.0
- Barium
- 8.0
- Temperature measurement
- 8.0
- Electric fields
- 6.0
- Basis sets
- 4.0

## Figures

Calculated RCCSD(T) potential energy curves for —see text for basis sets.

Calculated RCCSD(T) potential energy curves for —see text for basis sets.

Calculated RCCSD(T) potential energy curves for —see text for basis sets.

Calculated RCCSD(T) potential energy curves for —see text for basis sets.

Parallel and perpendicular temperatures for in He (313 K). Calculated values are shown by the solid line; experimental values from Ref. 8 are the points, with the error bars being the values. is given in Td.

Parallel and perpendicular temperatures for in He (313 K). Calculated values are shown by the solid line; experimental values from Ref. 8 are the points, with the error bars being the values. is given in Td.

Mobility of in He at 313 K. Calculated values are shown by the solid line; experimental values from Ref. 8 are the points. The bold error bars are the values reported in Ref. 8 , with the larger error bars being . is given in units of , is given in Td.

Parallel and perpendicular temperatures for in Ar (300 K). Calculated values are shown by the solid line; experimental values from Ref. 9 are the points, with the error bars being the values. is given in Td.

Parallel and perpendicular temperatures for in Ar (300 K). Calculated values are shown by the solid line; experimental values from Ref. 9 are the points, with the error bars being the values. is given in Td.

Mobility of in Ar at 300 K. Calculated values are shown by the solid line; experimental values from Ref. 8 are the points, with the error bars being the values. is given in units of , is given in Td.

Mobility of in Ar at 300 K. Calculated values are shown by the solid line; experimental values from Ref. 8 are the points, with the error bars being the values. is given in units of , is given in Td.

Skewness parameter, for in Ar. Calculated values are shown by the solid line; experimental values from Ref. 9 are the points, with the error bars being the values. is given in Td; the skewness is a dimensionless quantity.

Skewness parameter, for in Ar. Calculated values are shown by the solid line; experimental values from Ref. 9 are the points, with the error bars being the values. is given in Td; the skewness is a dimensionless quantity.

Mobility of in RG at 300 K. is given in units of , is given in Td.

Mobility of in RG at 300 K. is given in units of , is given in Td.

Mobility of in RG at 300 K. is given in units of , is given in Td.

Mobility of in RG at 300 K. is given in units of , is given in Td.

Comparison of mobility curves for (solid line) and (dashed line) in Ar. is given in units of , is given in Td. The right-hand trace is a zoom-in of the curve, showing the presence of a mobility minimum.

Comparison of mobility curves for (solid line) and (dashed line) in Ar. is given in units of , is given in Td. The right-hand trace is a zoom-in of the curve, showing the presence of a mobility minimum.

## Tables

Spectroscopic constants for calculated at the RCCSD(T) level—see text for basis sets. The quantities refer to the following isotopes: , , , , , and . Here, the symbols represent the usual spectroscopic quantities (Ref. 45 ): is the equilibrium bond length, is the depth of the potential; is the energy between the zero-point and the asymptote, is the harmonic vibrational frequency, is the anharmonicity constant, is the equilibrium rotational constant, is the vibration-rotation parameter, and is the harmonic force constant. The superscript “Morse” is self-explanatory.

Spectroscopic constants for calculated at the RCCSD(T) level—see text for basis sets. The quantities refer to the following isotopes: , , , , , and . Here, the symbols represent the usual spectroscopic quantities (Ref. 45 ): is the equilibrium bond length, is the depth of the potential; is the energy between the zero-point and the asymptote, is the harmonic vibrational frequency, is the anharmonicity constant, is the equilibrium rotational constant, is the vibration-rotation parameter, and is the harmonic force constant. The superscript “Morse” is self-explanatory.

Spectroscopic constants for calculated at the RCCSD(T) level—see text for basis sets. The quantities refer to the following isotopes: , , , , , and . Here, the symbols represent the usual spectroscopic quantities (Ref. 45 ); is the equilibrium bond length, is the depth of the potential; is the energy between the zero-point and the asymptote, is the harmonic vibrational frequency, is the anharmonicity constant, is the equilibrium rotational constant, is the vibration-rotation parameter, and is the harmonic force constant. The superscript Morse is self-explanatory.

Spectroscopic constants for calculated at the RCCSD(T) level—see text for basis sets. The quantities refer to the following isotopes: , , , , , and . Here, the symbols represent the usual spectroscopic quantities (Ref. 45 ); is the equilibrium bond length, is the depth of the potential; is the energy between the zero-point and the asymptote, is the harmonic vibrational frequency, is the anharmonicity constant, is the equilibrium rotational constant, is the vibration-rotation parameter, and is the harmonic force constant. The superscript Morse is self-explanatory.

Spectroscopic constants for calculated at the RHF and, in square brackets, the RCCSD(T) levels—see text for basis sets. The quantities refer to the following isotopes: , , , , , and . Here, the symbols represent the usual spectroscopic quantities (Ref. 45 ). RCCSD(T) values are taken from Table I .

Spectroscopic constants for calculated at the RHF and, in square brackets, the RCCSD(T) levels—see text for basis sets. The quantities refer to the following isotopes: , , , , , and . Here, the symbols represent the usual spectroscopic quantities (Ref. 45 ). RCCSD(T) values are taken from Table II .

Spectroscopic constants for calculated at the RHF and, in square brackets, the RCCSD(T) levels—see text for basis sets. The quantities refer to the following isotopes: , , , , , and . Here, the symbols represent the usual spectroscopic quantities (Ref. 45 ). RCCSD(T) values are taken from Table II .

Article metrics loading...

Full text loading...

Commenting has been disabled for this content