Analysis of spontaneous and laser emission from XeF

The B(1/2 2P3/2)→X(1/2 2Σ+) transition in XeBr

“…[15][16][17] Because the valence states arising from ground-term Rg and X atoms were expected to be bound by at most weak van der Waals forces, the charge-transfer ion-pair→valence transitions were predicted to be bound-free in nature. Indeed, the only exceptions to this picture appeared to be the B→X and D( 1 2 2 P 1/2 )→X transitions in XeCl, where fine violetdegraded band structure was observed, 5,18 and these same transitions in XeF, where quite rich discrete structure was manifested. [19][20][21][22][23] For XeBr ͑and most other RgX species͒ the high-pressure B→X spectrum seemed to show only soft undulatory structure, with intervals roughly marking the vibrational spacing in the excited state ͑Fig.…”

“…2 The essential spectroscopic features of the RgX molecules were quickly understood in terms of models which likened their ion-pair excited electronic states to the analogous alkali halide ground states and treated their valence states as essentially unbound. 1,[3][4][5][6][7][8] The strongest emission observed in high-pressure discharges was attributed to the B( 1 2 2 P 3/2 )→X( 1 2 2 ⌺ ϩ ) transition, 9 and lasing was eventually achieved on this transition in all the RgF and RgCl species for RgϭXe, Kr, and Ar. From a practical standpoint the XeBr laser has been far less significant than its RgF and RgCl cousins.…”

Spectroscopic studies of diatomic noble gas halides. II. Analysis of bound-free emission from XeBr, XeI, and KrF

“…(The value 136 cm-1 is 91% of w. for CsBr, which is the ratio found for XeCl vs CsCl. 12) As w~ increases, the subsidiary shoulders and peaks spread out and become more prominent, but decrease slightly in intensity, relative to the strong peak. These trends agree with qualitative expectations, Note, however, that the peak positions alone yield an incorrect description of the vibrational structure in the excited state, as they greatly exaggerate both the vibrational frequency and the anharmonicity.…”

“…Spectra were then computed for the five J values which represented the population medians for these segments. These J values are the solutions to the equations, f Y e-x dx = 1/10, 3/10, .•• ,9/10 , o (12) where y = BvJ(J + l)/kT. For the B state, Bv varies slowly enough with v to be approximated by Be in this calculation.…”

Neutral rare-gas containing charge-transfer molecules in solid matrices. II. HXeH, HXeD, and DXeD in Xe

“…The bonding in the HXY molecules can be understood in terms of their constituent ionic fragments X ϩ H and X ϩ Y Ϫ , which are both strongly bound. 3,4 Fajardo and Apkarian [5][6][7] have demonstrated that ultraviolet-irradiation of hydrogen halides in rare-gas matrices leads to permanent charge separation. The first step in that process is the photodissociation of a precursor, which yields separated hydrogen and halogen atoms isolated in a rare-gas environment.…”