Analyses of the excited 5f1 optical spectra of Th3+ compounds

Edelstein, Norman M.

doi:10.1016/j.cplett.2020.138317

Title: Analyses of the excited 5f¹ optical spectra of Th³⁺ compounds

Abstract

We look at the electronic structure of Th(Cp")₃ (Cp" = η⁵-C₅H₃(SiMe₃-1,3), a molecule which has a 6d¹ ground configuration and an excited 5f¹ configuration beginning approximately 14,000 cm^-1 higher, is reexamined. The ground state of the 6d¹ configuration in a crystal field of D_3h symmetry is shown to be an orbitally quenched ²A_1' state, best described as a pure ²D_1/2 state. Electric dipole selection rules from this state to the states for the 5f¹ configuration in a D_3h crystal field result in the 5f¹ truncated optical spectrum observed. The optical spectrum of the square planar Th³⁺ compound [Li(THF)₄][Th(OAr')₄], where (OAr' = OC₆ H₂tBu₂-2,6-Me-4), is discussed.

Authors:

^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Publication Date:: Tue Jan 05 00:00:00 EST 2021

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE

OSTI Identifier:: 1844379

Alternate Identifier(s):: OSTI ID: 1775641

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Chemical Physics Letters

Additional Journal Information:: Journal Volume: 767; Journal ID: ISSN 0009-2614

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Edelstein, Norman M. Analyses of the excited 5f1 optical spectra of Th3+ compounds.  United States: N. p., 2021. 
Web.  doi:10.1016/j.cplett.2020.138317.

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                    Edelstein, Norman M. Analyses of the excited 5f1 optical spectra of Th3+ compounds.  United States.  https://doi.org/10.1016/j.cplett.2020.138317

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                    Edelstein, Norman M. Tue .  
"Analyses of the excited 5f1 optical spectra of Th3+ compounds".  United States.  https://doi.org/10.1016/j.cplett.2020.138317.  https://www.osti.gov/servlets/purl/1844379.

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@article{osti_1844379,

  title        = {Analyses of the excited 5f1 optical spectra of Th3+ compounds},

  author       = {Edelstein, Norman M.},

  abstractNote = {We look at the electronic structure of Th(Cp")3 (Cp" = η5-C5H3(SiMe3-1,3), a molecule which has a 6d1 ground configuration and an excited 5f1 configuration beginning approximately 14,000 cm-1 higher, is reexamined. The ground state of the 6d1 configuration in a crystal field of D3h symmetry is shown to be an orbitally quenched 2A1' state, best described as a pure 2D1/2 state. Electric dipole selection rules from this state to the states for the 5f1 configuration in a D3h crystal field result in the 5f1 truncated optical spectrum observed. The optical spectrum of the square planar Th3+ compound [Li(THF)4][Th(OAr')4], where (OAr' = OC6 H2tBu2-2,6-Me-4), is discussed.},

  doi          = {10.1016/j.cplett.2020.138317},

  journal      = {Chemical Physics Letters},

  number       = ,

  volume       = 767,

  place        = {United States},

  year         = {Tue Jan 05 00:00:00 EST 2021},

  month        = {Tue Jan 05 00:00:00 EST 2021}

}

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Works referenced in this record:

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Similar Records

Title: Analyses of the excited 5f1 optical spectra of Th3+ compounds

Abstract

Citation Formats

Crystal field-spin orbit treatment in d1 and d9 trigonal bipyramidal complexes journal, October 1968

The 5 f →6 d absorption spectrum of Pa 4+ /Cs 2 ZrCl 6 journal, January 1992

The spectrum of trebly ionized thorium, Th IV journal, September 1949

The 6 d →5 f fluorescence spectra of PaCl 2− 6 in a Cs 2 ZrCl 6 crystal journal, January 1991

Absorption and Emission Spectra of Ce 3+ in Elpasolite Lattices journal, October 2003

The synthesis and characterisation, including X-ray diffraction study, of [Th{η-C 5 H 3 (SiMe 3 ) 2 } 3 ]; the first thorium( III ) crystal structure journal, January 1986

[Th(III)[.eta.5-C5H3(SiMe3)2]3], an actinide compound with a 6d1 ground state journal, February 1988

Absorption and Magnetic-Circular-Dichroism Spectra of Octahedral Ce 3 + in Cs 2 NaY Cl 6 journal, October 1973

Isolation of a Square-Planar Th(III) Complex: Synthesis and Structure of [Th(OC 6 H 2 t Bu 2 -2,6-Me-4) 4 ] 1– journal, July 2019

Relationship between the Coefficients of the Tensor Operator and Operator Equivalent Methods journal, November 1970

Electronic structure of f1 lanthanide and actinide complexes. Part 2. Non-relativistic and relativistic calculations of the ground state electronic structures and optical transition energies of [Ce(η-C5H5)3], [Th(η-C5H5)3] and [Pa(η-C8H8)2] journal, February 1997

Two-Photon Processes in Complex Atoms journal, October 1964

Anomalously small 4 f -5 d oscillator strengths and 4 f -4 f electronic Raman scattering cross sections for Ce 3 + in crystals of LuPO 4 journal, August 1989

Title: Analyses of the excited 5f¹ optical spectra of Th³⁺ compounds

Crystal field-spin orbit treatment in d1 and d9 trigonal bipyramidal complexes
journal, October 1968

The 5 f →6 d absorption spectrum of Pa ⁴⁺ /Cs ₂ ZrCl ₆
journal, January 1992

The spectrum of trebly ionized thorium, Th IV
journal, September 1949

The 6 d →5 f fluorescence spectra of PaCl ²⁻ ₆ in a Cs ₂ ZrCl ₆ crystal
journal, January 1991

Absorption and Emission Spectra of Ce ³⁺ in Elpasolite Lattices
journal, October 2003

The synthesis and characterisation, including X-ray diffraction study, of [Th{η-C ₅ H ₃ (SiMe ₃ ) ₂ } ₃ ]; the first thorium( III ) crystal structure
journal, January 1986

[Th(III)[.eta.5-C5H3(SiMe3)2]3], an actinide compound with a 6d1 ground state
journal, February 1988

Absorption and Magnetic-Circular-Dichroism Spectra of Octahedral ${Ce}^{3 +}$ in ${Cs}_{2}$ NaY ${Cl}_{6}$
journal, October 1973

Isolation of a Square-Planar Th(III) Complex: Synthesis and Structure of [Th(OC ₆ H ₂ ^t Bu ₂ -2,6-Me-4) ₄ ] ^1–
journal, July 2019

Relationship between the Coefficients of the Tensor Operator and Operator Equivalent Methods
journal, November 1970

Electronic structure of f1 lanthanide and actinide complexes. Part 2. Non-relativistic and relativistic calculations of the ground state electronic structures and optical transition energies of [Ce(η-C5H5)3], [Th(η-C5H5)3] and [Pa(η-C8H8)2]
journal, February 1997

Two-Photon Processes in Complex Atoms
journal, October 1964

Anomalously small 4 f -5 d oscillator strengths and 4 f -4 f electronic Raman scattering cross sections for ${Ce}^{3 +}$ in crystals of ${LuPO}_{4}$
journal, August 1989