Untitled

Solomonik, V. G.; Marochko, O. Yu.

doi:10.1023/a:1004834730711

Cited by 19 publications

(20 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The La and Lu outer atomic shells are described with Gaussian contracted functions basis sets [10]: on La atom (9 s 9 p 5 d ) [ [11]. The basis set on Lu atom is augmented with diffuse f -function with exponent 0.31 [11].…”

Section: Calculation Proceduresmentioning

confidence: 99%

“…The basis set on Lu atom is augmented with diffuse f -function with exponent 0.31 [11]. Valence shells of halide atoms F, Cl, Br, and I are described by 31G or 41G basis sets augmented with polarization d -functions with exponents 0.8 (F), 0.75(Cl) [12,6], 0.389 (Br), and 0.266 (I) [13,6].…”

Section: Calculation Proceduresmentioning

confidence: 99%

“…In addition, these basis sets were augmented with diffuse s -and p -functions with exponents 0.1076 (F), 0.0483 (Cl), 0.0376 (Br), 0.0368 (I) [12,6], and with f -function with exponent 1.49 (F), 0.65 (Cl), 0.50 (Br), 0.38 (I). The exponents of g -functions on metal atoms and of f -functions on halogen atoms were optimized in With the aim to compare the properties of Ln ions with those of the corresponding molecules LnX 3 , and to determine the energy of dissociation of ions within identical theoretical approximations (with the same effective core potentials and basis sets and using the same treatment of the electron correlation), we calculated the properties of LnX 3 molecules (the SDTQ-MP4 calculations were performed in this work, while the CISD+Q calculations were carried out in [11,15]). …”

Section: The Energies Of Dissociation Lnmentioning

confidence: 99%

“…However, according to the theoretical predictions, the PES minimum of some LnX 3 molecules corresponds to pyramidal geometry of nuclei with C 3v symmetry [11,15]. If this fact is taken into account, ∆E(1) will be lowered by the inversion barrier height h = E(D 3h ) -E(C 3v ) of LnX 3 molecule.…”

mentioning

confidence: 98%

“…The LaF 3 molecule has the highest inversion barrier among La and Lu trihalides. The inversion barrier in LaF 3 molecule is only 0.5 kJ/mol (CISD+Q method [11]). Since LnX 3 molecules have very small h, a nonplanar geometry of some LnX 3 molecules can be neglected.…”

mentioning

confidence: 99%

See 4 more Smart Citations

Structure, vibrational spectra, and energetic stability of LnX 4 − ions (Ln=La, Lu; X=F, Cl, Br, I)

2005

Self Cite

View full text Add to dashboard Cite

Molecular structure and properties of La and Lu tetrahalide ions (Ln ) are studied by the configuration interaction singles-and-doubles method augmented with quadruple excitation correction (CISD+Q) and by the fourth-order Möller-Plesset perturbation theory with account for single, double, triple, and quadruple excitations (SDTQ-MP4). The atomic inner shells are described by Stevens relativistic effective core potentials. Valence basis sets are augmented with diffuse s -, p -, and polarization d -, f -, and g -functions. The equilibrium configuration of nuclei in Ln ions was found to be tetrahedral. The equilibrium internuclear distances, quadratic force constants, vibrational frequencies, and IR intensities of Ln ions are compared with the corresponding parameters of La and Lu trihalide molecules (LnX 3 ), calculated within the same approximations. Regularities in the behavior of molecular parameters on going along the Ln LnC Ln Ln series and from La compounds to Lu compounds are revealed. Heights of the energy barriers to the Ln inversion through the square planar structures ( T d D 4 h T d ) are evaluated: 100-110 and 130-150 kJ/mol for La and Lu , respectively. Enthalpies of dissociation reactions Ln LnX 3 + Xare calculated and the results obtained are compared with the available experimental data.

show abstract

Section: Calculation Proceduresmentioning

confidence: 99%

Section: Calculation Proceduresmentioning

confidence: 99%

Section: The Energies Of Dissociation Lnmentioning

confidence: 99%

mentioning

confidence: 98%

mentioning

confidence: 99%

See 3 more Smart Citations

Structure, vibrational spectra, and energetic stability of LnX 4 − ions (Ln=La, Lu; X=F, Cl, Br, I)

2005

Self Cite

View full text Add to dashboard Cite

show abstract

Quantum Chemical Studies of Neutral and Ionized DyX, DyX₂, and DyX₃ Species (X = F, Cl, Br, I) and the Implications for the Mass Spectra of Gaseous DyX₃

et al. 2004

View full text Add to dashboard Cite

The mass spectrum pattern of DyF 3 (g) and the appearance potentials for identified ions were measured and compared with the respective data obtained previously for DyCl 3 , DyBr 3 , and DyI 3 . The structural parameters, total energies, and vibrational frequencies of DyX 3 , DyX 2 , and DyX (X = F, Cl, Br, I) neutral and single ionized species were determined by quantum-chemical studies. The theoretical appearance potentials of different ions, calculated from energies of gaseous species, are in the good agreement with the experimental data. Fragmentation energies of the DyX n + ion, where n = 1, 2, 3, were computed and compared with the mass spectra patterns of the respective vapour species. A theoretical electron population analysis indicates the involvement of the

show abstract

Ionic bonding of lanthanides, as influenced by d- and f-atomic orbitals, by core-shells and by relativity

Schwarz

et al. 2015

J. Comput. Chem.

View full text Add to dashboard Cite

Lanthanide trihalide molecules LnX3 (X = F, Cl, Br, I) were quantum chemically investigated, in particular detail for Ln = Lu (lutetium). We applied density functional theory (DFT) at the nonrelativistic and scalar and SO-coupled relativistic levels, and also the ab initio coupled cluster approach. The chemically active electron shells of the lanthanide atoms comprise the 5d and 6s (and 6p) valence atomic orbitals (AO) and also the filled inner 4f semivalence and outer 5p semicore shells. Four different frozen-core approximations for Lu were compared: the (1s(2) -4d(10) ) [Pd] medium core, the [Pd+5s(2) 5p(6) = Xe] and [Pd+4f(14) ] large cores, and the [Pd+4f(14) +5s(2) 5p(6) ] very large core. The errors of LuX bonding are more serious on freezing the 5p(6) shell than the 4f(14) shell, more serious upon core-freezing than on the effective-core-potential approximation. The LnX distances correlate linearly with the AO radii of the ionic outer shells, Ln(3+) -5p(6) and X(-) -np(6) , characteristic for dominantly ionic Ln(3+) -X(-) binding. The heavier halogen atoms also bind covalently with the Ln-5d shell. Scalar relativistic effects contract and destabilize the LuX bonds, spin orbit coupling hardly affects the geometries but the bond energies, owing to SO effects in the free atoms. The relativistic changes of bond energy BE, bond length Re , bond force k, and bond stretching frequency vs do not follow the simple rules of Badger and Gordy (Re ∼BE∼k∼vs ). The so-called degeneracy-driven covalence, meaning strong mixing of accidentally near-degenerate, nearly nonoverlapping AOs without BE contribution is critically discussed.

show abstract

Untitled

Cited by 19 publications

References 14 publications

Structure, vibrational spectra, and energetic stability of LnX 4 − ions (Ln=La, Lu; X=F, Cl, Br, I)

Structure, vibrational spectra, and energetic stability of LnX 4 − ions (Ln=La, Lu; X=F, Cl, Br, I)

Quantum Chemical Studies of Neutral and Ionized DyX, DyX₂, and DyX₃ Species (X = F, Cl, Br, I) and the Implications for the Mass Spectra of Gaseous DyX₃

Ionic bonding of lanthanides, as influenced by d- and f-atomic orbitals, by core-shells and by relativity

Contact Info

Product

Resources

About

Untitled

Cited by 19 publications

References 14 publications

Structure, vibrational spectra, and energetic stability of LnX 4 − ions (Ln=La, Lu; X=F, Cl, Br, I)

Structure, vibrational spectra, and energetic stability of LnX 4 − ions (Ln=La, Lu; X=F, Cl, Br, I)

Quantum Chemical Studies of Neutral and Ionized DyX, DyX2, and DyX3 Species (X = F, Cl, Br, I) and the Implications for the Mass Spectra of Gaseous DyX3

Ionic bonding of lanthanides, as influenced by d- and f-atomic orbitals, by core-shells and by relativity

Contact Info

Product

Resources

About

Quantum Chemical Studies of Neutral and Ionized DyX, DyX₂, and DyX₃ Species (X = F, Cl, Br, I) and the Implications for the Mass Spectra of Gaseous DyX₃