FORMALLY TETRAVALENT CERIUM AND THORIUM COMPOUNDS - A CONFIGURATION-INTERACTION STUDY OF CEROCENE CE(C8H8)(2) AND THOROCENE TH(C8H8)(2) USING ENERGY-ADJUSTED QUASI-RELATIVISTIC AB-INITIO PSEUDOPOTENTIALS
M. Dolg et al., FORMALLY TETRAVALENT CERIUM AND THORIUM COMPOUNDS - A CONFIGURATION-INTERACTION STUDY OF CEROCENE CE(C8H8)(2) AND THOROCENE TH(C8H8)(2) USING ENERGY-ADJUSTED QUASI-RELATIVISTIC AB-INITIO PSEUDOPOTENTIALS, Chemical physics, 195(1-3), 1995, pp. 71-82
Large-scale state-averaged multi-configuration self-consistent field,
configuration interaction, averaged coupled-pair functional and spin-o
rbit configuration interaction calculations have been carried out for
the ground states and low-lying excited states of the bis(cyclooctatet
raene)f-element sandwich complexes cerocene Ce(C8H8)(2) and thorocene
Th(C8H8)(2). Whereas for a single-determinant wavefunction thorocene m
ay be pictured as a Th-IV compound, i.e. a Th4+ closed-shell ion compl
exed by two aromatic C8H82- ligands, cerocene is to a first approximat
ion a Ce-III compound, i.e. a Ce3+ ion with a 4f(1) configuration and
two C8H81.5- ligands. When cerocene is described by a multi-determinan
t wavefunction admixture of the Ce4+ (C8H82-)(2) configuration leads t
o a (1)A(1g) ground state of the same symmetry as in thorocene. For bo
th compounds results for the metal-ring distance, the symmetric metal-
ring stretching frequency, the photoelectron spectrum and the optical
spectrum are compared to experimental data.