Electronic structures and bonding of CeF: A frozen-core four-component relativistic configuration interaction study

Yuko Wasada-Tsutsui, Yoshihiro Watanabe, Hiroshi Tatewaki

Research output: Contribution to journalArticle

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Abstract

We study the electronic structure of the ground and several low-lying states of the CeF molecule using Dirac-Fock-Roothaan (DFR) and four-component relativistic single and double excitation configuration interaction (SDCI) calculations in the reduced frozen-core approximation (RFCA). The ground state and two low-lying excited states are calculated to have (4f)1(5d)(6s) 1 configurations with Ω = 3.5, 4.5, and 3.5, and the resulting excitation energies, T0, are, respectively, 0.319 and 0.518 eV. The experimental configurations for these states are the same, although the experimental T0 values are ∼0.3 eV smaller than those calculated. Experimentally, the red-degraded band was observed to be 2.181 eV above the ground state, having the configuration (4f)1-(5d)1(6p) 1 with Ω = 4.5. The calculation for this state gives 2.197 eV and configuration (4f)1.0(5d)1.7(6p)0.3 with Ω = 4.5. We found that Ω, Re, and ν(1-0) obtained by CI agree well with experiment. Bonding between the Ce and the F is highly ionic. The 4f, 5d, and 6s valence electrons are localized at the Ce+ ion, because they are attracted by the Ce4+ ion core, and are excluded from the bonding region because of the electronic cloud around the negatively charged fluoride anion. The bonding in the ground and excited states of the CeF molecule is significantly influenced by the 6s and 5d electron distributions between the Ce and the F.

Original languageEnglish
Pages (from-to)8877-8883
Number of pages7
JournalJournal of Physical Chemistry A
Volume111
Issue number36
DOIs
Publication statusPublished - Sep 13 2007

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Ground state
configuration interaction
Electronic structure
electronic structure
Excited states
configurations
Ions
excitation
ground state
Molecules
Electrons
Excitation energy
Fluorides
Anions
electron distribution
fluorides
molecules
ions
anions
valence

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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Electronic structures and bonding of CeF : A frozen-core four-component relativistic configuration interaction study. / Wasada-Tsutsui, Yuko; Watanabe, Yoshihiro; Tatewaki, Hiroshi.

In: Journal of Physical Chemistry A, Vol. 111, No. 36, 13.09.2007, p. 8877-8883.

Research output: Contribution to journalArticle

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