Electronic structure of CeF from frozen-core four-component relativistic multiconfigurational quasidegenerate perturbation theory

Hiroshi Tatewaki, Shigeyoshi Yamamoto, Yoshihiro Watanabe, Haruyuki Nakano

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Abstract

We have investigated the ground state and the two lowest excited states of the CeF molecule using four-component relativistic multiconfigurational quasidegenerate perturbation theory calculations, assuming the reduced frozen-core approximation. The ground state is found to be (4 f1) (5 d1) (6 s1), with =3.5, where is the total electronic angular momentum around the molecular axis. The lowest excited state with =4.5 is calculated to be 0.104 eV above the ground state and corresponds to the state experimentally found at 0.087 eV. The second lowest excited state is experimentally found at 0.186 eV above the ground state, with =3.5 based on ligand field theory calculations. The corresponding state having =3.5 is calculated to be 0.314 eV above the ground state. Around this state, we also have the state with =4.5. The spectroscopic constants Re, ωe, and (1-0) calculated for the ground and first excited states are in almost perfect agreement with the experimental values. The characteristics of the CeF ground state are discussed, making comparison with the La F+ and LaF molecules. We denote the d - and f -like polarization functions as d* and f*. The chemical bond of CeF is constructed via { Ce3.6+ (5 p6 d*0.3 f*0.1) F0.6- (2 p5.6) }3+ formation, which causes the three valence electrons to be localized at Ce3.6+.

Original languageEnglish
Article number214901
JournalJournal of Chemical Physics
Volume128
Issue number21
DOIs
Publication statusPublished - Jun 13 2008

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Ground state
Electronic structure
perturbation theory
electronic structure
Excited states
ground state
excitation
Molecules
Angular momentum
Chemical bonds
chemical bonds
molecules
angular momentum
Polarization
Ligands
valence
ligands
Electrons
causes
polarization

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Electronic structure of CeF from frozen-core four-component relativistic multiconfigurational quasidegenerate perturbation theory. / Tatewaki, Hiroshi; Yamamoto, Shigeyoshi; Watanabe, Yoshihiro; Nakano, Haruyuki.

In: Journal of Chemical Physics, Vol. 128, No. 21, 214901, 13.06.2008.

Research output: Contribution to journalArticle

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