DOI: 10.1063/1.1670689. Optical Spectra of Os4+ in Single Cubic Crystals at 4.2°K

Optical Spectra of Os4+ in Single Cubic Crystals at 4.2°K

10.1063/1.1670689

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

The optical spectra of Os4+ (5d4) in single cubic crystals of K2PtCl6, Cs2ZrCl6, Cs2HfCl6, and Rb2ZrCl6 at 4.2°K has been studied. The spectrum is characterized by very narrow lines in the region from 10 000–36 000 cm−1. Vibrational structure is observed which may be assigned to the ungerade modes of the OsCl62− complex in the lattice. A crystal-field analysis within the d4 manifold fits the observed ten electronic, 0–0 transitions with an rms deviation of 228 cm−1 for the parameters A = 0, B = 741, C = 1296, V = 22490, and λ5d = 2416 cm−1. The calculated molar magnetic susceptibility agrees with that found for concentrated crystals such as K2OsCl6 and Cs2OsCl6. The analysis of the electronic states was dependent upon a calculation of intensities for the t2g4 → t2g3eg transitions. The calculated results are given for a tetragonal distortion of the cubic field and are shown to qualitatively agree with the linewidth of the transitions. The calculated g values for all observed transitions are tabulated. Finally, several conclusions about the optical spectra of 5d systems are presented.

Bibliography

Dorain, P. B., Patterson, H. H., & Jordan, P. C. (1968). Optical Spectra of Os4+ in Single Cubic Crystals at 4.2Â°K. The Journal of Chemical Physics, 49(9), 3845â3857.

Authors 3

Paul B. Dorain (first)
Howard H. Patterson (additional)
Peter C. Jordan (additional)

References 30 Referenced 75

{'key': '2024020904210011000_r1', 'first-page': '175', 'volume': '26', 'year': '1956', 'journal-title': 'Discussions Faraday Soc.'} / Discussions Faraday Soc. (1956)
10.1080/00268976000100231 / Mol. Phys. (1960)
10.3891/acta.chem.scand.17-1043 / Acta Chem. Scand. (1963)
10.1021/ic50005a020 / Inorg. Chem. (1963)
{'key': '2024020904210011000_r3'}
10.1063/1.1727734 / J. Chem. Phys. (1966)
10.1143/JPSJ.9.753 / J. Phys. Soc. Japan (1954)
10.1063/1.1733053 / J. Chem. Phys. (1962)
10.1080/00268975900100101 / Mol. Phys. (1959)
10.3891/acta.chem.scand.16-0793 / Acta Chem. Scand. (1962)
10.1021/ic50048a040 / Inorg. Chem. (1967)
{'key': '2024020904210011000_r10'}
10.1063/1.1725703 / J. Chem. Phys. (1964)
{'key': '2024020904210011000_r12', 'first-page': '1969', 'volume': '23A', 'year': '1967', 'journal-title': 'Spectrochim. Acta'} / Spectrochim. Acta (1967)
10.1063/1.1733502 / J. Chem. Phys. (1963)
10.1139/p65-135 / Can. J. Phys. (1965)
10.1063/1.1732614 / J. Chem. Phys. (1962)
10.1016/0371-1951(64)80066-7 / Spectrochim. Acta (1964)
10.1103/PhysRevLett.18.1054 / Phys. Rev. Letters (1967)
{'key': '2024020904210011000_r18'}
10.1016/0371-1951(63)80179-4 / Spectrochim. Acta (1963)
10.1524/zpch.1964.43.1_2.113 / Z. Physik. Chem. (Frankfurt) (1964)
{'key': '2024020904210011000_r21', 'first-page': '1251', 'volume': '108', 'year': '1957', 'journal-title': 'J. Chem. Phys.'} / J. Chem. Phys. (1957)
10.1063/1.1670690 / J. Chem. Phys. (1968)
10.1143/JPSJ.11.1171 / J. Phys. Soc. Japan (1956)
{'key': '2024020904210011000_r24'}
10.1139/v61-162 / Can. J. Chem. (1961)
{'key': '2024020904210011000_r26'}
{'key': '2024020904210011000_r27'}
{'key': '2024020904210011000_r28'}

Dates

Type	When
Created	21 years, 6 months ago (Feb. 6, 2004, 2:22 p.m.)
Deposited	1 year, 6 months ago (Feb. 8, 2024, 11:21 p.m.)
Indexed	1 year ago (Aug. 7, 2024, 4:30 a.m.)
Issued	56 years, 10 months ago (Nov. 1, 1968)
Published	56 years, 10 months ago (Nov. 1, 1968)
Published Print	56 years, 10 months ago (Nov. 1, 1968)

Funders 0

None

BibTeX

@article{Dorain_1968, title={Optical Spectra of Os4+ in Single Cubic Crystals at 4.2°K}, volume={49}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1670689}, DOI={10.1063/1.1670689}, number={9}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Dorain, Paul B. and Patterson, Howard H. and Jordan, Peter C.}, year={1968}, month=nov, pages={3845–3857} }

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  "abstract": "<jats:p>The optical spectra of Os4+\u2008(5d4) in single cubic crystals of K2PtCl6, Cs2ZrCl6, Cs2HfCl6, and Rb2ZrCl6 at 4.2\u00b0K has been studied. The spectrum is characterized by very narrow lines in the region from 10 000\u201336 000 cm\u22121. Vibrational structure is observed which may be assigned to the ungerade modes of the OsCl62\u2212 complex in the lattice. A crystal-field analysis within the d4 manifold fits the observed ten electronic, 0\u20130 transitions with an rms deviation of 228 cm\u22121 for the parameters A\u2009=\u20090, B\u2009=\u2009741, C\u2009=\u20091296, V\u2009=\u200922490, and \u03bb5d\u2009=\u20092416 cm\u22121. The calculated molar magnetic susceptibility agrees with that found for concentrated crystals such as K2OsCl6 and Cs2OsCl6. The analysis of the electronic states was dependent upon a calculation of intensities for the t2g4\u2009\u2192\u2009t2g3eg transitions. The calculated results are given for a tetragonal distortion of the cubic field and are shown to qualitatively agree with the linewidth of the transitions. The calculated g values for all observed transitions are tabulated. Finally, several conclusions about the optical spectra of 5d systems are presented.</jats:p>",
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