CASSCF and CASPT2 calculations for lanthanide trihalides LnX3 using model core potentials

Tsukamoto, Shinya; Mori, Hirotoshi; Tatewaki, Hiroshi; Miyoshi, Eisaku

doi:10.1016/j.cplett.2009.04.018

Cited by 16 publications

(23 citation statements)

References 31 publications

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“…Full geometry optimization and vibrational analysis of PrBr 3 were carried out, and the equilibrium structure and six normal coordinates Q i 's were obtained as shown in Figure 4. The optimized bond lengths of Pr-Br and the symmetry were 5.20 (Bohr) and D 3h , respectively, in good agreement with previously obtained results by Cundari et al 47 This bond length is also in reasonable agreement with a recent theoretical one, 5.15 (Bohr) with CASPT2, 48 and with the experimental one, 35 5.08 (Bohr). The frequency of each normal vibration, as shown in Table 4, is also in reasonable agreement with the experimental one.…”

Section: Oscillator Strengths Of Lanthanide Trihalidessupporting

confidence: 92%

Theoretical Study on the f−f Transition Intensities of Lanthanide Trihalide Systems

Hatanaka

Yabushita

2009

J. Phys. Chem. A

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The photoabsorption intensities of intra-4f(N) transitions (f-f transitions) in lanthanide systems have been extensively studied with the semiempirical Judd-Ofelt theory. The oscillator strengths of most f-f transitions are insensitive to a change of surrounding environment because 4f electrons are shielded by closed-shell 5s and 5p electrons from outside. However, there are some exceptional transitions, so-called hypersensitive transitions, whose intensities are very sensitive to a change of surrounding environment, and the reason for this hypersensitivity has not been clarified. In this study, we calculated the oscillator strengths of lanthanide trihalides (LnX(3); Ln = Pr, Tm; X = Br, I) with the multireference spin-orbit configuration interaction method and obtained reasonably accurate values. To clarify the cause of hypersensitivity, we examined various possible effects on the oscillator strengths, such as molecular vibration, f-d mixing, ligand to metal charge transfer (LMCT), and intraligand excitation, and concluded that the effect of molecular vibration is very small and that the oscillator strengths of most f-f transitions including hypersensitive transitions arise from both the LMCT and dynamic-coupled intraligand excitations through their configuration mixings with the dominant configurations of 4f(N).

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Section: Oscillator Strengths Of Lanthanide Trihalidessupporting

confidence: 92%

Theoretical Study on the f−f Transition Intensities of Lanthanide Trihalide Systems

Hatanaka

Yabushita

2009

J. Phys. Chem. A

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“…Recent work on lanthanide fluorides has focused on the determination of thermochemical, geometric, and electronic properties using highly correlated and multireference ab initio methods for lanthanide complexes . NdF 2+ was examined using complete active space SCF (CASSCF) and second‐order multiconurational quasi‐degenerate perturbation theory (MCQDPT2) and was found to have a very dense set of roughly parallel electronic states, similar to that found with PrF 2+ and PmF 2+ .…”

Section: Introductionmentioning

confidence: 90%

Dissociation energy and electronic structure of the low valent lanthanide compound NdF⁺

South

Schoendorff

Wilson

2016

Int J of Quantum Chemistry

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The electronic structure and dissociation energy of NdF+ are calculated using equation of motion completely renormalized coupled cluster theory [EOM‐CR‐CCSD(T)]. The potential energy curves of several of the lowest quintet and triplet states in each irreducible representation of C2v symmetry are calculated along with the dissociation energy of the ground quintet state of NdF+. The electronic structure and energies are then compared to those of the analogous compounds NdF2+ and NdF to understand the effect that the Nd 5d and 6s orbitals have on the chemical bonding environment. © 2016 Wiley Periodicals, Inc.

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“…For all geometry optimizations, we have used the cc-pVTZ basis set [22] for all atoms except lanthanide elements (Ce-Yb), which were described by the valence only relativistic model core potential (MCPtzp) [23][24][25] including a set of g-type polarization functions. All stationary points located on the potential energy surface (PES) were characterized as minima or first order transition states (TSs) through harmonic vibrational frequency calculations.…”

Section: Computational Detailsmentioning

confidence: 99%

Theoretical study of lanthanide mono cation-mediated C–F bond activation

Matsuda

Mori

2011

Chemical Physics

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CASSCF and CASPT2 calculations for lanthanide trihalides LnX3 using model core potentials

Cited by 16 publications

References 31 publications

Theoretical Study on the f−f Transition Intensities of Lanthanide Trihalide Systems

Theoretical Study on the f−f Transition Intensities of Lanthanide Trihalide Systems

Dissociation energy and electronic structure of the low valent lanthanide compound NdF⁺

Theoretical study of lanthanide mono cation-mediated C–F bond activation

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CASSCF and CASPT2 calculations for lanthanide trihalides LnX3 using model core potentials

Cited by 16 publications

References 31 publications

Theoretical Study on the f−f Transition Intensities of Lanthanide Trihalide Systems

Theoretical Study on the f−f Transition Intensities of Lanthanide Trihalide Systems

Dissociation energy and electronic structure of the low valent lanthanide compound NdF+

Theoretical study of lanthanide mono cation-mediated C–F bond activation

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Dissociation energy and electronic structure of the low valent lanthanide compound NdF⁺