Calculation of the structure, potential energy surface, vibrational dynamics, and electric dipole properties for the Xe:HI van der Waals complex

• Published in: The Journal of chemical physics 2011-05, Vol.134 (17), p.174302-174302-9
• Main Authors: Preller, M., Grunenberg, J., Bulychev, V. P., Bulanin, M. O.
• Format: Article
• Language: English
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.3583817

We report the structure and spectroscopic characteristics for the Xe:HI van der Waals binary isomers determined from variational solutions of two-dimensional and three-dimensional (3D) vibrational Schrödinger equations. The solutions are based on a potential energy surface computed at the coupled-cluster level of theory including single and double excitations and a non-iterative perturbation treatment of triple excitations [CCSD(T)]. The dipole moment surface was calculated using quadratic configuration interaction (QCISD). The global potential minimum is shown to be located at the anti-hydrogen-bonded Xe−IH isomer, 21 cm −1 below the secondary local minimum associated with the hydrogen-bonded Xe−HI isomeric form. The dissociation energy from the global minimum is 245.9 cm −1 . 3D Schrödinger equations are solved for the rotational quantum numbers J = k = 0, 1, and 2, without invoking an adiabatic separation of high- and low-frequency degrees of freedom. The vibrational ground state resides in the Xe−HI potential well, while the first excited state, 8.59 cm −1 above the ground, occupies the Xe−IH well. We find that intra-complex dynamics exhibits a sudden transformation upon increase of the r (HI) bond length, accompanied by abrupt changes in the geometric and dipole parameters. A similar chaotic behavior is predicted to occur for Xe:DI at a shorter r (DI) bond length, which implies stronger coupling between low- and high-frequency motions in the heavier complex. Our calculations confirm a strong enhancement for the r (HI) stretch fundamental and a significant weakening for the first overtone vibrational transitions in Xe:HI, as compared to those in the free HI molecule. A qualitative explanation of this, earlier experimentally detected effect is suggested.