Rotational spectra, potential function, Born–Oppenheimer breakdown and magnetic shielding of SiSe and SiTe

Giuliano, B. M.; Bizzocchi, L.; Grabow, Jens‐Uwe

doi:10.1016/j.jms.2008.03.008

Cited by 20 publications

(24 citation statements)

References 38 publications

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“…The conditions employed are apparently particularly favourable to the generation of excited vibrational states of PbI and InI. Excited vibrational states are commonly observed in spectra recorded for molecules generated through a combination of laser vaporization and supersonic expansion [20][21][22][23].…”

Section: Assignment Of the Rotational Spectra Of Vibrational Excited mentioning

confidence: 99%

Vibrational energies and full analytic potential energy functions of PbI and InI from pure microwave data

Yoo

Köckert

Mullaney

et al. 2016

Journal of Molecular Spectroscopy

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Pure rotational spectra of PbI and InI are interpreted to yield a full analytic potential energy function for each molecule. Rotational spectra for PbI have been retrieved from literature sources to perform the analysis. Rotational transition frequencies for excited vibrational states of InI (0 < v < 11) are measured during this work. Ignoring hyperfine splittings, B v and D v values are used to generate a set of "synthetic" pure R(0) transitions for each vibrational level. These are then fitted to an "Expanded Morse Oscillator" (EMO) potential using the direct-potential-fit program, DPOTFIT. The well-depth parameter, D e , is fixed at a literature value, while values of the equilibrium distance r e and EMO exponent-coefficient expansion (potential-shape) parameters are determined from the fits. Comparison with potential functions determined after including older mid-IR and visible electronic transition data shows that our analysis of the pure microwave data alone yields potential energy functions that accurately predict (to better than 1%) the overtone vibrational energies far beyond the range spanned by the levels for which the microwave data is available.

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Section: Assignment Of the Rotational Spectra Of Vibrational Excited mentioning

confidence: 99%

Vibrational energies and full analytic potential energy functions of PbI and InI from pure microwave data

Yoo

Köckert

Mullaney

et al. 2016

Journal of Molecular Spectroscopy

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“…[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.…”

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confidence: 99%

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

et al. 2015

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Reactions of [K(18-crown-6) anions, respectively.T he latter contains aP bSe ligand, ar ather uncommon homologue of CO that acts as a m-bridge between two Rh atoms.Q uantum chemical calculations yield asignificantly higher bond energy for PbSe than for CO,since the size of the ligand orbitals better matches the comparably rigid RhSe-Rh angles and the resulting Rh···Rh distance.T orationalize the bent coordination of the ligand, orbitals with significant ligand contributions and their dependence on the bonding angle were investigated in detail.The importance of CO,b oth as al igand and ar eactant, can hardly be overestimated. Thep ublication of at otal of 43 reviews in Angewandte Chemie,41in Chemical Reviews,and more than 50 in Coordination Chemistry Reviews within the last decade reflects the huge diversity of syntheses and catalytic applications of carbon monoxide and its compounds.In contrast, apart from matrix isolation experiments, [1] the molecular and coordination chemistry of the heavier homologues of CO,t hus the neutral molecular tetrel monochalcogenides E 14 E 16 (E 14 = C…Pb;E 16 = O…Te), with (formally) divalent E 14 (II) atoms,isrestricted to complexes with carbon monochalcogenides CS,C Se,a nd CTe.[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.[18] Nevertheless,according to calculations on PbO and PbS minerals,the nature and role of the lone pair at the Pb atom is strongly influenced by the corresponding chalcogenide ion, ranging from only small contributions of the 6s atomic orbital (due to the mixing of states) in PbO to arather high 6s contribution in the frontier orbital region of PbS. [19] Following this trend, ah igher electron density on the tetrel atom is expected for the heavier homologues of the PbE 16 series.T hus with E 16 = Se or Te, ligand activity might become possible,which will be discussed herein.In the synthesis of the mixed-valence compound [(RhPPh 3 ) 6 (m 3 -Se) 8 ]·0.5 en [20] 4 (m 3 -Se) 2 (m-PbSe)]} 2 ·1.3 en (1,F igure 1), as aw ell-reproducible side-product.Thea nion in 1 (Figure 1, top) is based on a[ Rh 3 Se 2 ] trigonal bipyramid, with two m 3 -Se bridges (Se1, Se2) in axial and three Rh atoms (Rh1-Rh3) in equatorial positions.A t first glance,t he Rh atoms adopt an approximately squareplanar coordination through two Se atoms (cis) and t...

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“…[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.…”

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“…[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.…”

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

et al. 2015

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Aus Reaktionen von [2a] Darüber hinaus gibt es Pinzettenkomplexe,i n denen SnO-oder PbO-Einheiten mithilfe von benzanellierten Bisstannylenliganden stabilisiert werden.[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. [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.[18] Rechnungen an PbO-und PbS-Mineralien zeigten, dass die Art und die Rolle des freien Elektronenpaars am PbAtom stark vom jeweiligen Chalkogenidion abhängt;inPbO führen Mischungen von Zuständen zu einem nur geringen Beitrag des 6s-Atomorbitals,w ährend der 6s-Beitrag im Grenzorbitalbereich von PbS relativ hoch ist.[

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Rotational spectra, potential function, Born–Oppenheimer breakdown and magnetic shielding of SiSe and SiTe

Cited by 20 publications

References 38 publications

Vibrational energies and full analytic potential energy functions of PbI and InI from pure microwave data

Vibrational energies and full analytic potential energy functions of PbI and InI from pure microwave data

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

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

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