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*Ab Initio* studies of the interaction potential for the Xe–NO(*X* ^{2}Π) van der Waals complex: Bound states and fully quantum and quasi-classical scattering

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10.1063/1.4731286

### Abstract

Adiabatic potential energy surfaces for the ground electronic state of the Xe⋅⋅⋅NO(*X* ^{2}Π) van der Waals complex have been calculated using the spin-restricted coupled cluster method with single, double, and non-iterative triple excitations (RCCSD(T)). The scalar relativistic effects present in the Xe atom were included by an effective core potential and we extended the basis with bond functions to improve the description of the dispersion interaction. It has been found that the global minimum on the *A* ^{′} adiabatic surface occurs at a T-shaped geometry with γ_{e} = 94° and *R* _{e} = 7.46 a_{0}, and with well depth of *D* _{e} = 148.68 cm^{−1}. There is also an additional local minimum for the collinear geometry Xe–NO with a well depth of 104.5 cm^{−1}. The adiabat of *A* ^{′′} symmetry exhibits a single minimum at a distance *R* _{e} = 7.68 a_{0} and has a skewed geometry with γ_{e} = 64° and a well depth of 148.23 cm^{−1}. Several *C* _{ nl } van der Waals dispersion coefficients are also estimated, of which *C* _{6, 0} and *C* _{6, 2} are in a reasonable agreement with previous theoretical results obtained by Nielson *et al.* [J. Chem. Phys.64, 2055 (1976)]10.1063/1.432428. The new potential energy surfaces were used to calculate bound states of the complex for total angular momentum quantum numbers up to *J* = 7/2. The ground stateenergy of Xe⋅⋅⋅NO(*X* ^{2}Π) is *D* _{0} = 117 cm^{−1}, which matches the experimental value very accurately (within 3.3%). Scattering calculations of integral and differential cross sections have also been performed using fully quantum close coupling calculations and quasi-classical trajectory method at a collision energy of 63 meV. These calculations reveal the important role played by *L*-type rainbows in the scattering dynamics of the heavier Rg–NO(*X*) systems.

© 2012 American Institute of Physics

Received 27 March 2012
Accepted 12 June 2012
Published online 06 July 2012

Acknowledgments: The support of the Spanish Ministry of Science and Innovation (to F.J.A. and M.M. via Grant Nos. CTQ2008-02578/BQU and CSD2009-00038) and of the UK EPSRC (to M.B. via Programme Grant No. EP/G00224X/1), the EU (to M.B. via FP7 EU People ITN Project No. 238671), and are gratefully acknowledged. J.K. acknowledges financial support from the US National Science Foundation (Grant No. CHE-0848110 to Professor M. H. Alexander) and the University Complutense de Madrid/Grupo Santander (under the “Movilidad de Investigadores Extranjeros” programme). We are grateful to Pablo Jambrina for help in some of the calculations.

Article outline:

I. INTRODUCTION

II. *AB INITIO* CALCULATIONS OF ADIABATIC POTENTIALS

A. Geometries, basis sets and method

B. Expansion and fitting of diabatic potentials

C. dispersion coefficients

III. FEATURES OF POTENTIAL ENERGY SURFACES

IV. BOUND STATES CALCULATIONS

V. QUASI-CLASSICAL TRAJECTORY(QCT) AND QUANTUM MECHANICAL (QM) SCATTERING CALCULATIONS

A. Quasi-classical trajectory calculation method

B. Fully quantum close coupling scattering method

VI. SCATTERING RESULTS

A. Integral cross sections

B. Opacity functions

C. Differential cross sections

VII. SUMMARY AND CONCLUSIONS

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2012-07-06

2014-04-17

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