TY - JOUR

T1 - Electronic structure of CeF from frozen-core four-component relativistic multiconfigurational quasidegenerate perturbation theory

AU - Tatewaki, Hiroshi

AU - Yamamoto, Shigeyoshi

AU - Watanabe, Yoshihiro

AU - Nakano, Haruyuki

N1 - Funding Information:
The authors thank Dr. H. Moriyama and Dr. Y. Wasada-Tsutsui for valuable discussion and for preparing some molecular data. Calculations were performed using the IBM p650 pSeries of the Library and Information Processing Center of Nagoya City University. The present work is supported by a Grant-in-Aid from the Ministry of Education, Culture, Sport, Science, and Technology (MEXT) of Japan.

PY - 2008

Y1 - 2008

N2 - 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+.

AB - 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+.

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U2 - 10.1063/1.2924118

DO - 10.1063/1.2924118

M3 - Article

C2 - 18537445

AN - SCOPUS:44849123475

SN - 0021-9606

VL - 128

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

IS - 21

M1 - 214901

ER -