Photoionization spectroscopy of Ga-rare gas complexes

Abstract

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Spectroscopy and calculations of weakly bound gallium complexes with ammonia and monomethylamine

“…19,31 An enhancement of metal-nitrogen binding upon a methyl substitution in NH 3 was also observed in sodium 32,33 and indium complexes. This trend is different from that in the M-Rg species ͑MϭAl, Ga, In; RgϭAr, Kr, Xe͒, 35 where the dispersion force is expected to be predominant. A Mulliken population analysis with the B3LYP method predicts that the orbital overlap between Ga and N is 0.13 in Ga-NH 3 and increases to 0.19 in Ga-NH 2 CH 3 .…”

Theoretical Study of M+−RG Complexes (M = Ga, In; RG = He−Rn)

“…This might be rationalized by noting that, because of the higher binding energy of Xe complexes, the interactions may be complicated by interloping states arising from higher asymptotes; such has been discussed recently by some of us in the case of the AuÀXe complex. 33,34 However, some caution is merited here for the Ga þ ÀRG complexes since the errors in the experimental dissociation energies 17 appear to be ca. 80À100 cm À1 .…”

“…The Ga(4 2 D 3/2,5/2 ) + RG asymptote can give rise to 2 Δ 3/2,5/2 , 2 Π 1/2,3/2 , and 2 Σ 1/2 + states, with the lowest energy states expected to be 2 Δ 3/2,5/2 . In Figure of ref are shown schematics of the orientation of the upper state 4d orbitals with respect to the internuclear axis, together with the outer s or p shells of the approaching RG atom. It is clear that the isotropic RG outer s or p shells can interact with the Ga + core more easily for the 2 Δ Ω states than they can for the 2 Π Ω states and, further, that the interaction for the 2 Σ + state is expected to be weak.…”

“…It is also of interest to compare the present results to the experimentally determined parameters for excited state neutral GaÀRG complexes using photoionization spectroscopy. Stangassinger et al 17 vaporized a gallium antimonide alloy rod, and mixed the metal vapor with an inert gas, or mixture of inert gases, before expanding into vacuum. The subsequent supersonic jet expansion led to the formation of GaÀRG complexes, which were internally cold.…”

“…We have used such methods in our previous work, where tests against mobility and spectroscopic data have shown that PECs obtained at these levels of theory are highly reliable. − (This comment applies to all-electron calculations, and those where “small-core” effective core potentials have been used; often the latter have necessitated augmentation of standard basis sets with tight basis functions to describe the outer-core/valence correlation.) Spectroscopic parameters have been determined from these potentials and are compared to the only previous reports of calculations on the Ga + −RG and In + −RG complexes: configuration interaction (CI) calculations by Dunning et al for Ga + −Ar and the results of a more recent CASSCF and MRCI study of Ga + −Ar by Park et al In addition, we shall compare the spectroscopic parameters we obtain for Ga + −RG to those obtained experimentally for excited states of Ga−RG obtained by Stangassinger et al, and our previously calculated results for the Tl + −RG complexes will be compared to those obtained, again experimentally, for the excited states of Tl−RG . Finally, we shall discuss trends in the values of the spectroscopic quantities in group 13 and present results on the transport coefficients.…”