Does the 4f-shell contribute to bonding in tetravalent lanthanide halides?

Journal Article · Sun Dec 28 00:00:00 EST 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4904722· OSTI ID:22415430

Ji, Wen-Xin ^[1]; Xu, Wei; Xiao, Yi; Wang, Shu-Guang ^[1]

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1. School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 200240 Shanghai (China)

Lanthanide tetrahalide molecules LnX{sub 4} (Ln = Ce, Pr, Tb; X = F, Cl, Br, I) have been investigated by density functional theory at the levels of the relativistic Zero Order Regular Approximation and the relativistic energy-consistent pseudopotentials, using frozen small- and medium-cores. The calculated bond lengths and vibrational frequencies are close to the experimental data. Our calculations indicate 4f shell contributions to bonding in LnX{sub 4}, in particular for the early lanthanides, which show significant overlap between the Ln 4f-shell and the halogen np-shells. The 4f shells contribute to Ln-X bonding in LnX{sub 4} about one third more than in LnX{sub 3}.

• OSTI ID: 22415430
• Journal Information: Journal of Chemical Physics, Vol. 141, Issue 24; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
APPROXIMATIONS
BOND LENGTHS
BONDING
CERIUM FLUORIDES
DENSITY FUNCTIONAL METHOD
MOLECULES
POTENTIALS
PRASEODYMIUM CHLORIDES
RELATIVISTIC RANGE
TERBIUM BROMIDES