Infrared-active spin-orbit transitions of halogen atom dopants in solid parahydrogen: The role of trapping site geometry

Abstract

We present theoretical calculations of the 2P1/2 ← 2P3/2 spin-orbit transition of Cl dopants embedded as substitutional impurities in solid parahydrogen (pH2) matrices. In the lower-energy 2P3/2 spin-orbit level, the Cl atom's electron density distribution is anisotropic, and slightly distorts the geometry of the atom's trapping site. This distortion leads to a blue shift in the spin-orbit transition energy; the blue shift is enhanced when we account for the large-amplitude zero point motions of the pH2 molecules surrounding the Cl dopant. We also show that the intensity of the transition depends on the geometry of the trapping site. In the gas phase, the 2P1/2 ← 2P3/2 atomic transition is electric dipole forbidden. However, when the Cl atom resides in trapping sites that mimic the hexagonal close packed morphology of pure solid pH2, the transition becomes electric dipole allowed through interaction-induced transition dipole moments. These transition dipole moments originate in the anisotropic electron density distribution of the lower-energy 2P3/2 spin-orbit level. © 2013 AIP Publishing LLC.