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

Abstract

Photolysis of hydrogen halides ͑and some other hydrogen containing small molecules͒ in solid Xe yields in a two step process charged centers, one of them being XeHXe ϩ . Annealing of the irradiated doped solids produces, in addition to H-Xe-Y ͑YϭCl, Br, or I͒ species characterized by us previously, a fairly strong doublet at 1181 and 1166 cm Ϫ1 and a weak absorption at 701 cm Ϫ1 . Deuterated precursors yield a doublet at 846 and 856 cm Ϫ1 . Also peaks belonging to mixed H/D form are found, indicating that the absorbing species contains two H/D atoms. The new species responsible for these absorptions are assigned as neutral linear centrosymmetric HXeH, HXeD, and DXeD. The nature of the bonding can be understood in terms of the resonance between the two ionic forms HXe ϩ H Ϫ and H Ϫ Xe ϩ H, analogously to the valence bond description of the well known XeF 2 . The pseudopotential ͑LANL1DZ͒ ab initio calculations at the MP2 level are in good agreement with the observed spectra.

An aromatic noble-gas hydride: C6H5CCXeH

“…For a PhAc/Xe matrix photolyzed at 250 nm, annealing at about 40 K particularly leads to the formation of the known species HXeH (1181.2 and 1166.4 cm −1 ) 44 . In addition, several previously unreported bands also appear upon annealing at temperatures activating H-atom mobility (Fig.…”

HXeI and HXeH in Ar, Kr, and Xe matrices: Experiment and simulation

“…The interval between the two bands of HXeH in a Kr matrix is about 18 cm −1 , i.e., similar to the interval between the two HXeH bands observed in a Xe matrix (15 cm −1 ). 2 It is possible that the origin of this splitting in Kr and Xe matrices is similar.…”

“…1 As an exception, the HXeH molecule does not contain an electronegative fragment. 2 These metastable molecules can be prepared by UV photolysis of a HY precursor in a Ng matrix and subsequent thermal mobilization of the H atoms, which leads to the reaction of the neutral fragments H + Ng + Y → HNgY. Due to weak bonding and large dipole moments, the HNgY molecules are strongly affected by interaction with other species (N 2 , CO 2 , H 2 O, etc.).…”

Structure and Stability of (NG)nCN3Be3+ Clusters and Comparison with (NG)BeY0/+

“…However, in 1933 Pauling [2] hinted at the possibility of chemical bond formation for the bottom elements of Group 18 in the periodic table, as the large distance between their outermost electronic shells and their nuclei makes the outer electrons loosely bound. Räsänen and coworkers [10][11][12][13][14][15][16][17] successfully synthesized a series of compounds of type HXY (X = NG atom; Y = electron-withdrawing group) by photodissociation of HY in a NG matrix at low temperatures. Prompted by this discovery, [3,4] within a very short period, successful preparations of a number of krypton, xenon, and radon compounds [5][6][7][8] were reported.…”

“…[9] During the recent years, the chemistry of NG compounds has been significantly enriched by the fruitful outcome of scientists' efforts. Räsänen and coworkers [10][11][12][13][14][15][16][17] successfully synthesized a series of compounds of type HXY (X = NG atom; Y = electron-withdrawing group) by photodissociation of HY in a NG matrix at low temperatures. Two articles by Christe [18] and Gerber [19] entitled "A Renaissance in Noble Gas Chemistry" and "New Chemistry of the Noble Gas Elements: Novel Molecules, Polymers and Crystals" review the recent achievements in NG chemistry.…”