Radiative lifetimes for the B-X transition in HgCl, HgBr, and HgI

Physics – Chemical Physics

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Electron Transitions, Mercury Compounds, Metal Halides, Radiative Lifetime, Charge Transfer, Laser Materials, Mathematical Models, Molecular Energy Levels, Transition Probabilities

Scientific paper

The paper describes a charge transfer model which was used to calculate the radiative lifetimes for the B-X (lasing) transition in HgCl, HgBr, and HgI. The transition between the ionic upper state and the covalent ground state is viewed as a 'one-electron jump', in which the active electron jumps from the negative halogen ion into the hole in the valence shell of the positively-charged mercury ion. Electric dipole matrix elements in the Hg-halides have been calculated by means of a one-electron charge transfer theory. The upper and lower states are predominantly ionic and covalent, respectively, but it is necessary to allow for mixing between these states in order to obtain reasonable results. Expressions for the mixed X and B state wavefunctions and for the transition dipole moment are presented, and the importance of some neglected effects is estimated.

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