Calculation for the charge-transfer effect of La compounds in the 3d-1 core-hole state

Chikashi Suzuki, T. Mukoyama, Jun Kawai, Hirohiko Adachi

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Abstract

We calculate the electronic structures of La halides and oxides from a first-principles calculation by the spin-unrestricted DV-Xα molecular-orbital method of model clusters. The model clusters we use are [LaO6]9-, [LaF6]3-, [LaCl6]-3, and [LaBr6]3-, as model clusters of La2O3, LaF3, LaCl3., and LaBr3, respectively. The electronic structures of these clusters are calculated for the ground state and the 3d-1 core-hole states. The 3d-1 core-hole states can be regarded as the final states of La 3d x-ray photoemission spectroscopy (XPS), and the creation of 3d-1 core-hole states induces the charge-transfer effect. It is found from these calculations that, due to the charge-transfer effect, the numbers of unpaired 4f electrons in the 3d-1 core-hole states of [LaCl6]3-, [LaBr6]3-, [LaF6]3-, and [LaO6]9- increase by 1.10, 1.15, 0.37, and 0.58, respectively, from the ground state. From this result, it is found that charge-transfer effect ordering is [LaBr6]3- = [LaCl6]3->[LaO6]9->[LaF 6]3-. La 3d XPS of La halides and oxides was reported [S. Suzuki, T. Ishii, and T. Sagawa, J. Phys. Soc. Jpn. 37, 1334 (1974); J. C. Fuggle et al., Phys. Rev. Lett. 45, 1597 (1980)], and the intensity ratios of the high- to low-binding-energy peaks of La 3d XPS for LaCl3, LaBr3, LaF3, and La2O3 are 1.4, 1.4, 0.3. and 0.8 in case of both 3d5/2 and 3d3/2 XPS, which means that the core-hole screening ordering is LaBr3=LaCl3>La2O3>LaF 3. From these results, it is found that the intensity ratio of the high- to low-binding-energy peak of La 3d XPS among La compounds corresponds to the charge-transfer effect.

Original languageEnglish
Pages (from-to)9507-9514
Number of pages8
JournalPhysical Review B - Condensed Matter and Materials Physics
Volume57
Issue number16
Publication statusPublished - Apr 15 1998

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Photoelectron spectroscopy
Charge transfer
photoelectric emission
charge transfer
X rays
spectroscopy
Binding energy
x rays
Oxides
Ground state
Electronic structure
halides
binding energy
electronic structure
ground state
oxides
Molecular orbitals
molecular orbitals
Screening
screening

ASJC Scopus subject areas

  • Condensed Matter Physics

Cite this

Calculation for the charge-transfer effect of La compounds in the 3d-1 core-hole state. / Suzuki, Chikashi; Mukoyama, T.; Kawai, Jun; Adachi, Hirohiko.

In: Physical Review B - Condensed Matter and Materials Physics, Vol. 57, No. 16, 15.04.1998, p. 9507-9514.

Research output: Contribution to journalArticle

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abstract = "We calculate the electronic structures of La halides and oxides from a first-principles calculation by the spin-unrestricted DV-Xα molecular-orbital method of model clusters. The model clusters we use are [LaO6]9-, [LaF6]3-, [LaCl6]-3, and [LaBr6]3-, as model clusters of La2O3, LaF3, LaCl3., and LaBr3, respectively. The electronic structures of these clusters are calculated for the ground state and the 3d-1 core-hole states. The 3d-1 core-hole states can be regarded as the final states of La 3d x-ray photoemission spectroscopy (XPS), and the creation of 3d-1 core-hole states induces the charge-transfer effect. It is found from these calculations that, due to the charge-transfer effect, the numbers of unpaired 4f electrons in the 3d-1 core-hole states of [LaCl6]3-, [LaBr6]3-, [LaF6]3-, and [LaO6]9- increase by 1.10, 1.15, 0.37, and 0.58, respectively, from the ground state. From this result, it is found that charge-transfer effect ordering is [LaBr6]3- = [LaCl6]3->[LaO6]9->[LaF 6]3-. La 3d XPS of La halides and oxides was reported [S. Suzuki, T. Ishii, and T. Sagawa, J. Phys. Soc. Jpn. 37, 1334 (1974); J. C. Fuggle et al., Phys. Rev. Lett. 45, 1597 (1980)], and the intensity ratios of the high- to low-binding-energy peaks of La 3d XPS for LaCl3, LaBr3, LaF3, and La2O3 are 1.4, 1.4, 0.3. and 0.8 in case of both 3d5/2 and 3d3/2 XPS, which means that the core-hole screening ordering is LaBr3=LaCl3>La2O3>LaF 3. From these results, it is found that the intensity ratio of the high- to low-binding-energy peak of La 3d XPS among La compounds corresponds to the charge-transfer effect.",
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AU - Adachi, Hirohiko

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N2 - We calculate the electronic structures of La halides and oxides from a first-principles calculation by the spin-unrestricted DV-Xα molecular-orbital method of model clusters. The model clusters we use are [LaO6]9-, [LaF6]3-, [LaCl6]-3, and [LaBr6]3-, as model clusters of La2O3, LaF3, LaCl3., and LaBr3, respectively. The electronic structures of these clusters are calculated for the ground state and the 3d-1 core-hole states. The 3d-1 core-hole states can be regarded as the final states of La 3d x-ray photoemission spectroscopy (XPS), and the creation of 3d-1 core-hole states induces the charge-transfer effect. It is found from these calculations that, due to the charge-transfer effect, the numbers of unpaired 4f electrons in the 3d-1 core-hole states of [LaCl6]3-, [LaBr6]3-, [LaF6]3-, and [LaO6]9- increase by 1.10, 1.15, 0.37, and 0.58, respectively, from the ground state. From this result, it is found that charge-transfer effect ordering is [LaBr6]3- = [LaCl6]3->[LaO6]9->[LaF 6]3-. La 3d XPS of La halides and oxides was reported [S. Suzuki, T. Ishii, and T. Sagawa, J. Phys. Soc. Jpn. 37, 1334 (1974); J. C. Fuggle et al., Phys. Rev. Lett. 45, 1597 (1980)], and the intensity ratios of the high- to low-binding-energy peaks of La 3d XPS for LaCl3, LaBr3, LaF3, and La2O3 are 1.4, 1.4, 0.3. and 0.8 in case of both 3d5/2 and 3d3/2 XPS, which means that the core-hole screening ordering is LaBr3=LaCl3>La2O3>LaF 3. From these results, it is found that the intensity ratio of the high- to low-binding-energy peak of La 3d XPS among La compounds corresponds to the charge-transfer effect.

AB - We calculate the electronic structures of La halides and oxides from a first-principles calculation by the spin-unrestricted DV-Xα molecular-orbital method of model clusters. The model clusters we use are [LaO6]9-, [LaF6]3-, [LaCl6]-3, and [LaBr6]3-, as model clusters of La2O3, LaF3, LaCl3., and LaBr3, respectively. The electronic structures of these clusters are calculated for the ground state and the 3d-1 core-hole states. The 3d-1 core-hole states can be regarded as the final states of La 3d x-ray photoemission spectroscopy (XPS), and the creation of 3d-1 core-hole states induces the charge-transfer effect. It is found from these calculations that, due to the charge-transfer effect, the numbers of unpaired 4f electrons in the 3d-1 core-hole states of [LaCl6]3-, [LaBr6]3-, [LaF6]3-, and [LaO6]9- increase by 1.10, 1.15, 0.37, and 0.58, respectively, from the ground state. From this result, it is found that charge-transfer effect ordering is [LaBr6]3- = [LaCl6]3->[LaO6]9->[LaF 6]3-. La 3d XPS of La halides and oxides was reported [S. Suzuki, T. Ishii, and T. Sagawa, J. Phys. Soc. Jpn. 37, 1334 (1974); J. C. Fuggle et al., Phys. Rev. Lett. 45, 1597 (1980)], and the intensity ratios of the high- to low-binding-energy peaks of La 3d XPS for LaCl3, LaBr3, LaF3, and La2O3 are 1.4, 1.4, 0.3. and 0.8 in case of both 3d5/2 and 3d3/2 XPS, which means that the core-hole screening ordering is LaBr3=LaCl3>La2O3>LaF 3. From these results, it is found that the intensity ratio of the high- to low-binding-energy peak of La 3d XPS among La compounds corresponds to the charge-transfer effect.

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