Vibrational spectrum and force field of osmium tetroxide

McDowell, Robin S.; Goldblatt, Maxwell

doi:10.1021/ic50097a037

Cited by 96 publications

(27 citation statements)

References 2 publications

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“…33 Whereas their frequencies are well known from experiment, 33 much less precise information on their intensities is available, see Table I. 33 Whereas their frequencies are well known from experiment, 33 much less precise information on their intensities is available, see Table I.…”

Section: The Static Dipole Polarizability Of Osomentioning

confidence: 99%

Dipole-quadrupole and dipole-octopole polarizability of OsO4 from depolarized collision-induced light scattering experiments, ab initio and density functional theory calculations

Hohm

Maroulis

2004

The Journal of Chemical Physics

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The dipole-quadrupole and dipole-octopole polarizability of osmium tetroxide (OsO(4)) has been determined from collision-induced light-scattering experiments. Our final estimates for these properties are |A|=(84+/-5)e(2)a(3)(0)E(-1)(h) and |E|=(214+/-25)e(2)a(4)(0)E(-1)(h). We have also analyzed previous experimental data of the relative permittivity and refractivity of OsO(4) to propose the electronic part of the static dipole polarizability of alpha=51.0e(2)a(2)(0)E(-1)(h). To support our findings we have performed high-level ab initio and density functional theory calculations to obtain theoretical static estimates alpha=(50.2+/-1.6)e(2)a(2)(0)E(-1)(h), A=(84+/-10)e(2)a(3)(0)E(-1)(h), and E=(-252+/-32)e(2)a(4)(0)E(-1)(h), in essential agreement with the proposed experimental values.

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Section: The Static Dipole Polarizability Of Osomentioning

confidence: 99%

Dipole-quadrupole and dipole-octopole polarizability of OsO4 from depolarized collision-induced light scattering experiments, ab initio and density functional theory calculations

Hohm

Maroulis

2004

The Journal of Chemical Physics

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“…Subsequent Raman studies of the vapour by Huston and Claassen [14] yielded v Z ( E ) at 333.1 cm-' and vq(T2) at 322.7 cm-', but according to McDowell and Goldblatt [15] the IR spectrum of the vapour shows the Q branch of v, at 329.0cm-'. Subsequent Raman studies of the vapour by Huston and Claassen [14] yielded v Z ( E ) at 333.1 cm-' and vq(T2) at 322.7 cm-', but according to McDowell and Goldblatt [15] the IR spectrum of the vapour shows the Q branch of v, at 329.0cm-'.…”

Section: Osomentioning

confidence: 99%

Raman and IR spectra of matrix isolated OsO₃F₂ AND OsO₄: The molecular shape of monomeric OsO₃F₂

Beattle¹,

Blayden²,

Crocombe³

et al. 1976

J Raman Spectroscopy

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This paper reports fundamental vibration frequencies for molecular OS03Fz and o s o 4 isolated in argon matrices at low temperatures. Os03Fz is shown to have D3h symmetry on the basis of Raman and IR selection rules, and this conclusion is confirmed by the results of ' 8 0 enrichment studies which demonstrate the presence of an oso3 unit containing three equivalent oxygens. The argon matrix frequencies are 946.5 ( A ; ) , 928.5 (E'), 646 (A;), 619 ( A ; ) 348 (E"), 316.5 (E') 258 ( A ; ) and 206 (E') cm-l. High resolution spectra are also reported for matrix isolated oS1604 (~1963, vz 332, v3 956, and v4 327 cm-I) and for ' 8 0 enriched oso4 species.

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“…The lowest energy transition centred at -33 800 cm-' exhibits a long vibrational progression in the gas phase, with a separation of -813cm-' [25] this being either the a, or tz M -0 stretching mode. Day [22] has observed a change in both the mcd and absorption spectra after the first five members of this progression and has suggested the possibility of there being two separate electronic transitions under the 33 800 cm-absorption envelope.…”

Section: Osmium Tetroxidementioning

confidence: 97%

“…The weaker secondary features observed in the early members of the progression have the same vibrational separation as the principle members and are separated from them by -340cm-'. Thus these bands are presumably due to a, or t, progressions built onto the electronic origin plus one quantum of an e or t2 M -0 bending mode [25]. The question still remains as to whether the first band at -33 800 cm-is one electronic transition with severe Jahn-Teller distortion or whether there are two separate electronic transitions.…”

Section: Osmium Tetroxidementioning

confidence: 99%

Applications of the Matrix Isolation Technique in Magnetic Circular Dichroism Spectroscopy

Barton

Douglas

Grinter

et al. 1976

Ber Bunsenges Phys Chem

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Problemstellung : orbital angular momentum.Prof. H.: The measurement of g values might yield the Antwort des Vortragenden: P. J. Z.: There seems to be a g value shift in coronene anion which is larger than would correspond with spin orbit coupling. If this extra shift is due to (1,) and in which kind of fashion is not clear. Diskussionsredner : Prof. Buckingham Diskussionsbeitrag zum Vortrag von Herrn P. J. Zandstra Problemstellung : Prof. B.: Is it possible t o determine the orbital angular momentum by two other methods: esr or the Zeeman effect? Antwort des Vortragenden : P. J. Z.: I n esr one measures spin flips independent of the value (f 1, ) of the orbital angular momentum. It is not certain which interaction term of the Hamiltonian might yield a n effect on the g-value. In similar cases of transition metal ions only the effect of 1s coupling seems to have been considered.The only remaining technique might be the measurement of the static susceptibility. Attempts in our laboratory so far did not succeed, because it was not possible to prepare sufficiently high concentrations.The compounds are reactive to an extent which makes it difficult if not impossible t o study the crystalline state, thus Zeeman type measurements are perhaps not possible. Apparate und Methoden 1 Benzol J Matrix-Isolation / MCD J Osmium TetroxidAn apparatus for the measurement of the magnetic circular dichroism (mcd) spectra of matrix-isolated species between 14 and 50 K is described. Some examples of the spectra obtained are shown. The application of these measurements to the interpretation of the vibrational structure of electronic spectra is illustrated using benzene and osmium tetroxide as examples.Ein Apparat fur die Messung yon magnetischen Zirkulardichroismus-Spektren (mcd) der matrixisolierten Substanzen zwischen 14 und 50 K wird beschrieben. Ein paar Beispiele der erhaltenen Spektren werden gezeigt. Die Verwendung dieser Messungen zur Erklarung der Schwingungsstruktur der elektronischen Spektren wird mit Hilfe der Beispiele Benzol und Osmiumtetroxyd veranschaulicht.

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Vibrational spectrum and force field of osmium tetroxide

Cited by 96 publications

References 2 publications

Dipole-quadrupole and dipole-octopole polarizability of OsO4 from depolarized collision-induced light scattering experiments, ab initio and density functional theory calculations

Dipole-quadrupole and dipole-octopole polarizability of OsO4 from depolarized collision-induced light scattering experiments, ab initio and density functional theory calculations

Raman and IR spectra of matrix isolated OsO₃F₂ AND OsO₄: The molecular shape of monomeric OsO₃F₂

Applications of the Matrix Isolation Technique in Magnetic Circular Dichroism Spectroscopy

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Vibrational spectrum and force field of osmium tetroxide

Cited by 96 publications

References 2 publications

Dipole-quadrupole and dipole-octopole polarizability of OsO4 from depolarized collision-induced light scattering experiments, ab initio and density functional theory calculations

Dipole-quadrupole and dipole-octopole polarizability of OsO4 from depolarized collision-induced light scattering experiments, ab initio and density functional theory calculations

Raman and IR spectra of matrix isolated OsO3F2 AND OsO4: The molecular shape of monomeric OsO3F2

Applications of the Matrix Isolation Technique in Magnetic Circular Dichroism Spectroscopy

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Raman and IR spectra of matrix isolated OsO₃F₂ AND OsO₄: The molecular shape of monomeric OsO₃F₂