Relativistic configuration interaction calculations on the low-lying electronic states of Hl

✍ Scribed by D.A. Chapman; K. Balasubramanian; S.H. Lin

• Publisher: Elsevier Science
• Year: 1985
• Tongue: English
• Weight: 307 KB
• Volume: 118
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(85)85296-9

✦ Synopsis

Relativisuc configuration interaction calculations are described for stx low-lying elertroruc states of J-II. The spearox+ proper~~~ or these states are calculated and compared with available experimental results. 1_ Intioduction The hydrogen iodide molecule has been of considerable experimental and theoretical interest for a number of years [ l-6]_ The reported electronic spectra of HI consist of absorption continua near 46000 cm-l [7] and 23000 cm-l [8], as well as absorption bands which extend from approxunately 55555 cm-l to above the first dissociation limit [ l,S] _ The first ultraviolet continuum is broad and featureless, peaking around 45000 cm-l [6]. Mulliken [3] has assigned this absorption as due to three transitions: the parallel transition l E+ p' + %a', and two per-p endicular transitions 1X& + II1 and lZ& + %I1 [6]. Clear, Riley and Wilson [6] have described photofragmentation spectroscopy studres of HI and DI photolysis at 37550 cm-l in which the absorption continuum is decomposed into contributions from the 31T1, 3n,-,+ and lllr states. Huber and Henberg [9] have assigned these states to an absorption continuum starting at approximately 28000 cm-l with maximum absorption at approxrmately 46000 cm-l The interest in performing relativistic calculations on the HI molecule arises as a result of the large spinorbit interactron present in the iodine atom. The HI molecule has a closed-shell ground state, and promotion of erther a u or rr electron to the antibonding a* orbital leads to 9 X-s states which are split by spin-orbit interaction into 14 w--w states (see table 1) ' Alfred P. Sl-Fellow_