Solid parahydrogen matrices that contain open-shell (2P) Cl or Br dopants as substitutional impurities exhibit several infrared absorption features associated with (i) spin-orbit excitation of the halogen atom; (ii) vibrational excitation of one of the H2 molecules near the halogen atom; or (iii) simultaneous spin-orbit excitation of the halogen atom and vibrational excitation of a nearby H2 molecule.  A detailed analysis of these spectral features provides information about the van der Waals well in the entrance channel of the halogen + H2 potential energy surface, and in particular about the coupling, in this region of the surface, between the halogen atom's electronic degrees of freedom and the nuclear degrees of freedom of its H2 neighbors.  We present an analysis of these spectral features based on quantum Monte Carlo simulations that accurately incorporate the large-amplitude zero point motion of individual H2 molecules in the solid.

Infrared-active spin-orbit transitions of Cl and Br dopants in solid parahydrogen

245th National Meeting (2013)

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