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- Title
Structure, force fields, and vibrational spectra of cerium tetrahalides.
- Authors
Solomonik, V. G.; Yachmenev, A. Yu.; Smirnov, A. N.
- Abstract
The geometrical structure, force fields, and vibrational spectra of CeX4 (X = F, Cl, Br, I) were investigated by second, third, and fourth order Möller-Plesset perturbation theory, CISD+Q configuration interaction method, and the CCSD(T) coupled cluster method. Calculations on CeF4 were also performed by multiconfiguration second order perturbation theory MCQDPT2/CASSCF. The wave function of the ground state of CeX4 molecules was found to be appreciably non-one-configurational; this property increases from cerium fluorides to iodides and leads to the divergence of the series of Möller-Plesset perturbation theory. The calculated data point to a tetrahedral equilibrium nuclear configuration in CeX4 molecules. The energy barriers to the inversion of the tetrahedral CeX4 molecules via the square configurations are high enough, 74–89 kJ/mol. The calculated vibration frequencies, effective internuclear distances, and mean amplitudes of nuclear vibrations in CeF4 agree with IR and Raman spectroscopic and high-temperature gas-phase electron diffraction data.
- Subjects
PERTURBATION theory; CLUSTER analysis (Statistics); WAVE functions; CERIUM; ELECTRON diffraction; RAMAN spectroscopy
- Publication
Journal of Structural Chemistry, 2008, Vol 49, Issue 4, p613
- ISSN
0022-4766
- Publication type
Article
- DOI
10.1007/s10947-008-0085-5