The rotational spectra, potential function, Born–Oppenheimer breakdown, and hyperfine structure of GeSe and GeTe

Abstract

The pure rotational spectra of 18 and 21 isotopic species of GeSe and GeTe have been measured in the frequency range 5-24 GHz using a Fabry-Pérot-type resonator pulsed-jet Fourier-transform microwave spectrometer. Gaseous samples of both chalcogenides were prepared by a combined dc discharge/laser ablation technique and stabilized in supersonic jets of Ne. Global multi-isotopologue analyses of the derived rotational data, together with literature high-resolution infrared data, produced very precise Dunham parameters, as well as rotational constant Born-Oppenheimer breakdown (BOB) coefficients (δ(01)) for Ge, Se, and Te. A direct fit of the same datasets to an appropriate radial Hamiltonian yielded analytic potential-energy functions and BOB radial functions for the X(1)Σ(+) electronic state of both GeSe and GeTe. Additionally, the electric quadrupole and magnetic hyperfine interactions produced by the nuclei (73)Ge, (77)Se, and (125)Te were observed, yielding much improved quadrupole coupling constants and first determinations of the spin-rotation parameters.

{μ‐PbSe}: A Heavy CO Homologue as an Unexpected Ligand

“…Furthermore, SnO and PbO units were stabilized within pincer complexes using benzannulated bisstannylene ligands 2b. All other examples were only discussed as intermediates in the context of spectroscopic3–6 and/or theoretical studies,4–16 such as molecular PbO which was obtained under single‐atom‐collision conditions from atomic Pb and O 3 17…”

“…[2a] Furthermore,S nO and PbO units were stabilized within pincer complexes using benzannulated bisstannylene ligands. [2b] All other examples were only discussed as intermediates in the context of spectroscopic [3][4][5][6] and/or theoretical studies, [4][5][6][7][8][9][10][11][12][13][14][15][16] such as molecular PbO which was obtained under single-atom-collision conditions from atomic Pb and O 3 . [17] Ther eason for the apparent difference between the chemistry of CO and that of its heavier homologues has been attributed to the distinctly lower bond strength of the corresponding "triple" bond with increasing atomic number, and therefore ah igher tendencyt owards aggregationultimately yielding the respective minerals,s uch as litharge and massicot in the case of PbO.…”

Heavier congeners of CO and CO2 as ligands: from zero-valent germanium (‘germylone’) to isolable monomeric GeX and GeX2 complexes (X = S, Se, Te)

“…It has been shown that the molecular variants of EX and EX 2 can exist in condensed cryogenic matrices at very low temperature or diluted in the gas phase at high temperature. Thus they have solely been detected spectroscopically 2 under extreme conditions or proposed as reactive intermediates 3 and studied by theoretical calculations. 4 …”

μ‐PbSe: ein schweres CO‐Homolog als ungewöhnlicher Ligand

“…[2b] Alle anderen Vertreter traten entweder im Verlauf von spektroskopischen Experimenten als Intermediate auf [3][4][5][6] und/oder wurden in theoretischen Studien behandelt. [4][5][6][7][8][9][10][11][12][13][14][15][16] Molekulares PbO beispielsweise konnte in Einzelatomkollisionsexperimenten aus Pb-Atomen und O 3 erhalten werden.…”

“…[4][5][6][7][8][9][10][11][12][13][14][15][16] Molekulares PbO beispielsweise konnte in Einzelatomkollisionsexperimenten aus Pb-Atomen und O 3 erhalten werden. [17] Der Grund für diesen offensichtlichen Unterschied zwischen der Chemie von CO und seinen schwereren Homologen wird auf die deutlich geringere Bindungsenergie der "Dreifachbindung" mit steigender Ordnungszahl und der daraus resultierenden grçßeren Aggregationsneigung zurückgeführt, die letztendlich zur Bildung der entsprechenden Mineralien wie Lithargit oder Massicotit im Falle des PbO führt.…”