Characterization of the molecular iodine electronic wave functions and potential energy curves through hyperfine interactions in the B0+_u(3Pi_u) state

Abstract

We present a high-resolution analysis of the six electronic states that share the same dissociation limit with the second excited electronic state B in molecular iodine. These six states are coupled to the B state via hyperfine interactions. The four hyperfine parameters, C B , ␦ B , d B , and eqQ B , are calculated with the available potential energy curves and wave functions constructed from the separated-atom basis set. We obtain a maximum separation of the respective contributions from all six electronic states and compare each individual contribution with high-precision spectroscopic data, providing an independent verification of the relevant electronic structure.

Laser-induced atomic fragment fluorescence spectroscopy: A facile technique for molecular spectroscopy of spin-forbidden states

“…Suitable molecules include homonuclear and heteronuclear alkali dimers, 28,29 and possibly more generally, molecules such as I 2 , ICN, and alkyl iodides that commonly photodissociate into ground-state I ͑ 2 P 3/2 ͒ and excited-state I ‫ء‬ ͑ 2 P 1/2 ͒. [30][31][32] In the present experiment, laser power broadening precluded full rotational resolution of the P and R branches for the spin-forbidden b 3 ⌸ ⍀u state. The experimental sensitivity may easily be improved however, e.g., by using faster optics ͑we have built an f / 1 optical system instead of the f / 4 system used in this study͒ and/or more sensitive and faster fluorescence detection.…”

The hyperfine structure of 129 I 2 and 127 I 129 in the B band system

“…The coefficients lk can also be related to the potential of the electronic state, and a power expansion of with the internuclear distance R can be derived. Such an approach was recently used by Chen et al [6,7] and earlier by Spirko and Blabla [20]. For the sake of simplicity of recalculation by other researchers, however, we shall follow the Dunham approach.…”

“…They also applied successfully a different approach to the description of the rovibrational dependence of the hyperfine parameters, which accounts for the dependence of the hyperfine interactions on the internuclear distance averaged over the vibrational motion. In that framework observations close to the dissociation limit could be modelled by including distinct electronic states sharing the same asymptote, and the resulting perturbations in the upper levels of the B 3 Å 0 þ u [7]. Thus, new data are available offering the possibility to extend models of the hyperfine structure in the B-X system.…”

Raman spectroscopy of iodine molecules trapped in zeolite crystals

“…[10][11][12][13] Their hyperfine optical transitions 14 have been used to lock a molecular optical clock with higher precision than most rf atomic clocks. 15 However, limited by the vapor pressure, a free-space-based iodine molecular optical clock normally requires a long ͑ϳ1 m͒ vapor cell.…”