Abstract

<i>Ab initio</i> Hartree—Fock calculations in the single-configuration approximation predict that the 3<i>s</i> 3<i>p</i><sup>6 2</sup><i>S</i><sub>½</sub> level of Cl <sub>I</sub> lies far above the ionization limit, although this level is observed to be the lowest of all even <i>J</i> = 1/2 levels other than 3<i>s</i><sup>2</sup> 3<i>p</i><sup>4</sup> 4<i>s</i><sup>4</sup><i>P</i><sub>½</sub>, <sup>2</sup><i>P</i><sub>½</sub>. The solution of this anomaly lies in configuration interaction with the high-lying portion of the 3<i>s</i><sup>2</sup> 3<i>p</i><sup>4</sup> ∊<i>d</i><sup>2</sup><i>S</i><sub>½</sub> continuum, which is sufficiently strong to depress the computed <i>s p</i><sup>6</sup> level to its observed position. This interaction with the continuum is an extension of the well-known interaction of <i>sp</i><sup>ω + 1</sup> with the discrete <i>s</i><sup>2</sup><i>p</i><sup>ω - 1</sup><i>nd</i> Rydberg series, and is important in all neutral third-row elements Al to Cl, as well as in Br and I and probably other fourth- and fifth-row elements. The effect is, however, somewhat smaller in Br <sub>1</sub> and I <sub>1</sub> than in Cl <sub>1</sub>, with the result that there exists no bromine nor iodine level that is primarily <i>sp</i><sup>6</sup> in nature. The interactions produce large changes in computed transition probabilities and photoionization cross sections.

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