### Abstract

A first-principles, fully relativistic, many electron method was applied to the calculation of the multiplet energies in the KLL Auger transition of 3d transition metals from chromium to copper (Z=24-29). The method is a configuration interaction (CI) method, combined with a fully relativistic molecular orbital (MO) theory using four-component MOs. Coulomb and spin-orbit interactions are fully considered in the active CI space with no adjustable parameters. All integrals in matrix elements are numerically calculated. The models of a free atom and a metal cluster having 13-19 atoms were used. The calculated multiplet splittings showed a systematic increase as the atomic number increased over the range from the KL_{23}L_{23}, KL _{1}L_{23}, to the KL_{1}L_{1} configurations. The trend originated from the increase in orbital contraction. The results obtained using metal clusters had smaller multiplet splittings between the ^{3}P_{2}(KL_{3}L_{3}) and ^{1}S _{0}(KL_{2}L_{2}) terms than in the case of free-atom models by about 0.2eV. Two final-state configurations were compared to see the effect of CI in the KL_{23}L_{23} multiplets. The calculated energies were well comparable to the experimentally obtained peak positions. The ^{1}S_{0} terms largely shifted by the inclusion of the CI with the KL_{1}L_{1} configuration.

Original language | English |
---|---|

Pages (from-to) | 451-455 |

Number of pages | 5 |

Journal | Journal of Electron Spectroscopy and Related Phenomena |

Volume | 137-140 |

Issue number | SPEC. ISS. |

DOIs | |

Publication status | Published - Jul 2004 |

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### Keywords

- First-principles calculation
- Fully relativistic calculation
- KLL Auger spectra
- Molecular orbital
- Multiplet structure

### ASJC Scopus subject areas

- Physical and Theoretical Chemistry
- Spectroscopy
- Atomic and Molecular Physics, and Optics
- Surfaces and Interfaces

### Cite this

*Journal of Electron Spectroscopy and Related Phenomena*,

*137-140*(SPEC. ISS.), 451-455. https://doi.org/10.1016/j.elspec.2004.02.064

**First-principles calculation of the KLL Auger transition energy in 3d transition metals.** / Ishii, T.; Kövér, L.; Berényi, Z.; Cserny, I.; Ikeno, H.; Adachi, H.; Drube, W.

Research output: Contribution to journal › Article

*Journal of Electron Spectroscopy and Related Phenomena*, vol. 137-140, no. SPEC. ISS., pp. 451-455. https://doi.org/10.1016/j.elspec.2004.02.064

}

TY - JOUR

T1 - First-principles calculation of the KLL Auger transition energy in 3d transition metals

AU - Ishii, T.

AU - Kövér, L.

AU - Berényi, Z.

AU - Cserny, I.

AU - Ikeno, H.

AU - Adachi, H.

AU - Drube, W.

PY - 2004/7

Y1 - 2004/7

N2 - A first-principles, fully relativistic, many electron method was applied to the calculation of the multiplet energies in the KLL Auger transition of 3d transition metals from chromium to copper (Z=24-29). The method is a configuration interaction (CI) method, combined with a fully relativistic molecular orbital (MO) theory using four-component MOs. Coulomb and spin-orbit interactions are fully considered in the active CI space with no adjustable parameters. All integrals in matrix elements are numerically calculated. The models of a free atom and a metal cluster having 13-19 atoms were used. The calculated multiplet splittings showed a systematic increase as the atomic number increased over the range from the KL23L23, KL 1L23, to the KL1L1 configurations. The trend originated from the increase in orbital contraction. The results obtained using metal clusters had smaller multiplet splittings between the 3P2(KL3L3) and 1S 0(KL2L2) terms than in the case of free-atom models by about 0.2eV. Two final-state configurations were compared to see the effect of CI in the KL23L23 multiplets. The calculated energies were well comparable to the experimentally obtained peak positions. The 1S0 terms largely shifted by the inclusion of the CI with the KL1L1 configuration.

AB - A first-principles, fully relativistic, many electron method was applied to the calculation of the multiplet energies in the KLL Auger transition of 3d transition metals from chromium to copper (Z=24-29). The method is a configuration interaction (CI) method, combined with a fully relativistic molecular orbital (MO) theory using four-component MOs. Coulomb and spin-orbit interactions are fully considered in the active CI space with no adjustable parameters. All integrals in matrix elements are numerically calculated. The models of a free atom and a metal cluster having 13-19 atoms were used. The calculated multiplet splittings showed a systematic increase as the atomic number increased over the range from the KL23L23, KL 1L23, to the KL1L1 configurations. The trend originated from the increase in orbital contraction. The results obtained using metal clusters had smaller multiplet splittings between the 3P2(KL3L3) and 1S 0(KL2L2) terms than in the case of free-atom models by about 0.2eV. Two final-state configurations were compared to see the effect of CI in the KL23L23 multiplets. The calculated energies were well comparable to the experimentally obtained peak positions. The 1S0 terms largely shifted by the inclusion of the CI with the KL1L1 configuration.

KW - First-principles calculation

KW - Fully relativistic calculation

KW - KLL Auger spectra

KW - Molecular orbital

KW - Multiplet structure

UR - http://www.scopus.com/inward/record.url?scp=2942558644&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=2942558644&partnerID=8YFLogxK

U2 - 10.1016/j.elspec.2004.02.064

DO - 10.1016/j.elspec.2004.02.064

M3 - Article

AN - SCOPUS:2942558644

VL - 137-140

SP - 451

EP - 455

JO - Journal of Electron Spectroscopy and Related Phenomena

JF - Journal of Electron Spectroscopy and Related Phenomena

SN - 0368-2048

IS - SPEC. ISS.

ER -