Titanium(IV) chloride at 150 K

Dawson, Alice; Parkin, Andrew; Parsons, Simon; Pulham, Colin R.; Young, Alex

doi:10.1107/s1600536802016665

Cited by 7 publications

(6 citation statements)

References 5 publications

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“…A series of metal tetrachlorides were constructed according to experimental X-ray structures, − and the Cl K-edge TDDFT XAS spectra were calculated with the BP86 functional , and TZVP basis set following ref . XAS pre-edge features for five metal tetrachlorides ([CuCl 4 ] 2– , [NiCl 4 ] 2– , [CoCl 4 ] 2– , [FeCl 4 ] 2– , [TiCl 4 ] 0 ) were calculated using ES-TDDFT with initial guess transitions originating from core orbitals.…”

Section: Benchmarks and Discussionmentioning

confidence: 99%

Energy-Specific Linear Response TDHF/TDDFT for Calculating High-Energy Excited States

Liang

Fischer

Frisch³

et al. 2011

J. Chem. Theory Comput.

106

135

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An energy-specific TDHF/TDDFT method is introduced in this article for excited state calculations. This approach extends the conventional TDHF/TDDFT implementation to obtain excited states above a predefined energy threshold. The method introduced and developed in this work enables computationally efficient yet rigorous calculations of energy-specific spectra, e.g., X-ray absorption involving extremely high-energy transitions. All transitions are solved in the full molecular orbital space, and orthogonality to the ground state and lower-lying excited states is preserved for each high-energy excited state. Encouraging computational savings are observed in calculating the targeted energy spectrum, while the transition energies, as well as oscillator strengths, remain identical to the results from the standard implementation.

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Section: Benchmarks and Discussionmentioning

confidence: 99%

Energy-Specific Linear Response TDHF/TDDFT for Calculating High-Energy Excited States

Liang

Fischer

Frisch³

et al. 2011

J. Chem. Theory Comput.

106

135

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show abstract

“…The latter was needed because PBE fails to produce a gap for TiCl 2 and, for some orderings of the Ti magnetic moments, also for TiCl 3 . Experimental crystal structures were used without further relaxation. − For the MgCl 2 slab models with TiCl 2 at the edges, however, we had to relax the structure (for details see Section S6 of the Supporting Information). NMR chemical shieldings were calculated with the gauge-including PAW method of refs , as implemented in VASP and using PBE.…”

Section: Methodsmentioning

confidence: 99%

Preactive Site in Ziegler–Natta Catalysts

Blaakmeer¹,

Wensink²,

Eck³

et al. 2019

J. Phys. Chem. C

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Ziegler−Natta catalysts are one of the most important industrial catalysts for the production of isotactic polypropylene, yet they are still not properly understood at the molecular level. We explore the potential of 35,37 Cl and 47,49 Ti solid-state NMR to study the formation of catalytically relevant titanium sites. First, a systematic study of titanium chlorides (TiCl 2 , TiCl 3 , and TiCl 4 ) is undertaken to gain insight into the spectral characteristics for different titanium coordinations. For these materials, chlorine spectra can be relatively straightforwardly obtained, despite their strongly broadened quadrupolar line shapes. The sensitivity of titanium NMR to its local environment is exemplified by the TiCl 4 spectrum, for which a small quadrupolar interaction is found despite the nearly symmetric Ti coordination. Upon wet impregnation of MgCl 2 with TiCl 4 , TiCl 4 is immobilized at the surface, retaining its tetrahedral coordination. For a ball-milled binary MgCl 2 /TiCl 2 adduct, a ternary system where donors are added, and a ternary system where Al-alkyl cocatalysts are added, we obtain broad 47,49 Ti spectra after extensive signal averaging, showing that the local environment of Ti is substantially perturbed. The span of the signal is similar for all three samples, suggesting that most of the donor and the cocatalyst do not directly bind to the titanium. Nevertheless, the signal loss from reduction to Ti 3+ is obvious, indicating that a fraction of the titanium sites is activated.

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“…The Ti–Cl distances (216.4(2) pm) and Cl–Ti–Cl angles (108.7(1)–109.9(1)°) are similar to TiCl 4 (Ti–Cl: 216.3–216.5 pm, Cl–Ti–Cl: 108.9–109.9°). 13 A mixed molecular compound and co-crystallization of TeCl 4 and TiCl 4 , to the best of our knowledge, is observed here for the first time. An isolated (TeCl 4 ) 4 tetramer was not observed in a compound until now (except for pure TeCl 4 itself).…”

Section: Resultsmentioning

confidence: 50%

(TeCl)₄(TiCl₄) with isolated Te₄Cl₁₆ and TiCl₄ molecules and second-harmonic-generation

Bonnin,

Beier,

Bayarjargal

et al. 2024

Dalton Trans.

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Titanium(IV) chloride at 150 K

Cited by 7 publications

References 5 publications

Energy-Specific Linear Response TDHF/TDDFT for Calculating High-Energy Excited States

Energy-Specific Linear Response TDHF/TDDFT for Calculating High-Energy Excited States

Preactive Site in Ziegler–Natta Catalysts

(TeCl)₄(TiCl₄) with isolated Te₄Cl₁₆ and TiCl₄ molecules and second-harmonic-generation

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Titanium(IV) chloride at 150 K

Cited by 7 publications

References 5 publications

Energy-Specific Linear Response TDHF/TDDFT for Calculating High-Energy Excited States

Energy-Specific Linear Response TDHF/TDDFT for Calculating High-Energy Excited States

Preactive Site in Ziegler–Natta Catalysts

(TeCl)4(TiCl4) with isolated Te4Cl16 and TiCl4 molecules and second-harmonic-generation

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(TeCl)₄(TiCl₄) with isolated Te₄Cl₁₆ and TiCl₄ molecules and second-harmonic-generation