Thermodynamic properties of lanthanide trihalide molecules

Myers, Clifford E.; Graves, Dana T.

doi:10.1021/je60075a016

Cited by 66 publications

(45 citation statements)

References 6 publications

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“…Table III collects the harmonic wave numbers for the two series of lanthanide molecules, together with the experimental data, either measured or estimated. 15 The agreement with experimental data is satisfactory for both sets of RECPs considered in the present study, the mean absolute error being about 19 cm −1 . Similar errors, even if obtained over a smaller set of molecules, are found at the MP2 (18 cm −1 ) and at the CAS (13 cm −1 ) level.…”

Section: Pbe0supporting

confidence: 78%

“…24,25 The largest deviations from experimental data are found for some low frequencies, which have not been measured directly, but only estimated by an extrapolation procedure. 15 For instance, the ν2 mode of LuF 3 and the ν3 mode of LuBr 3 are underestimated by 66 and 62 cm −1 , respectively. Because similar differences are found at any level of computation, including post-HF methods, a revision of the extrapolated frequencies might be in order.…”

Section: Pbe0mentioning

confidence: 96%

See 1 more Smart Citation

Structures and properties of lanthanide and actinide complexes by a new density functional approach: Lanthanum, gadolinium, lutetium, and thorium halides as case studies

Adamo¹,

Barone²

2000

J. Comput. Chem.

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ABSTRACT:The LaX 3 , GdX 3 , LuX 3 , and ThX 4 systems (X = F, Cl, Br, and I) have been chosen as test cases to analyze the performances of a computational protocol, resting on a recently proposed density functional method, the so-called PBE0 model. Relativistic effects were taken into account by means of two different sets of quasi-relativistic effective core potentials. All static data were found to be in very good agreement with those provided by post-HF methods. Because experimental geometries have been determined at high temperature (1000-1800 K), the effect of nuclear motions have been considered through a variational numerical procedure.

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Section: Pbe0supporting

confidence: 78%

Section: Pbe0mentioning

confidence: 96%

Structures and properties of lanthanide and actinide complexes by a new density functional approach: Lanthanum, gadolinium, lutetium, and thorium halides as case studies

Adamo¹,

Barone²

2000

J. Comput. Chem.

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“…The interatomic distances and angles were estimated on the basis of the geometry given in Ref. 10 for DyBr 3 ͑g͒ as ͑Dy-Br͒ b ϭ2.88 Å, ͑Dy-Br͒ t ϭ2.62 Å, ՄBr b DyBr b ϭ115°, and ՄBr t DyBr t ϭ108°. The indices t and b denote terminal or bridge bonds for the distances and terminal or bridge positions of atoms.…”

Section: Discussionmentioning

confidence: 99%

Vaporization of DyBr3(s) and thermochemistry of the dimer homocomplex (DyBr3)2(g)

Hilpert

Miller

Ramondo³

1995

The Journal of Chemical Physics

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Thermochemistry of the molecule (ZnI2)2(g) and the vaporization of ZnI2(s)The vaporization of DyBr 3 ͑s͒ was investigated in the temperature range between 803 and 1053 K by Knudsen effusion mass spectrometry. The ions Dy ϩ , DyBr ϩ , DyBr 2 ϩ , DyBr 3 ϩ , Dy 2 Br 5 ϩ , and Br ϩ were detected and their appearance potentials determined leading to an upper bound for the atomization energy of DyBr 3 ͑g͒. The species DyBr 3 ͑g͒ and ͑DyBr 3 ͒ 2 ͑g͒ were identified in the vapor and their partial pressures determined using quantitative vaporization. Enthalpies and entropies of sublimation resulted according to the second-law and third-law methods. The enthalpy and entropy changes of the dissociation reaction ͑DyBr 3 ͒ 2 ͑g͒ ϭ 2 DyBr 3 ͑g͒ were obtained as ⌬ d H 298 0 ϭ220.8Ϯ6.6 kJ mol Ϫ1 and ⌬ d S 298 0 ϭ163.7Ϯ8.5 J mol Ϫ1 K Ϫ1 .

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“…This view has sometimes been refuted, while d covalence is generally accepted for the lanthanides. 1,4,5,[19][20][21][22][23][24] The 4f shell is not always considered as corelike for the whole row. The early and later lanthanide elements, e.g., Ce and Lu, usually play different roles in bonding.…”

Section: Introductionmentioning

confidence: 99%

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

Xiao

et al. 2014

The Journal of Chemical Physics

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Lanthanide tetrahalide molecules LnX4 (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 LnX4, 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 LnX4 about one third more than in LnX3.

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Thermodynamic properties of lanthanide trihalide molecules

Cited by 66 publications

References 6 publications

Structures and properties of lanthanide and actinide complexes by a new density functional approach: Lanthanum, gadolinium, lutetium, and thorium halides as case studies

Structures and properties of lanthanide and actinide complexes by a new density functional approach: Lanthanum, gadolinium, lutetium, and thorium halides as case studies

Vaporization of DyBr3(s) and thermochemistry of the dimer homocomplex (DyBr3)2(g)

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

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