Molecular orbitals and photoelectron spectra of some titanium(IV) organometallic compounds

Basso-Bert, Mario; Cassoux, P.; Crasnier, François; Gervais, D.; Labarre, Jean‐François; Loth, Philippe De

doi:10.1016/s0022-328x(00)82118-x

Cited by 15 publications

(7 citation statements)

References 26 publications

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“…The O br C bond length of 139 pm in the first configuration (O br ‐CH 2 ‐O ip ) also suggests single‐bond character. The TiC bond of the second configuration is 210 pm, close to distances found for Ti IV –compounds 67…”

Section: Resultssupporting

confidence: 80%

The Role of Surface and Subsurface Point Defects for Chemical Model Studies on TiO₂: A First‐Principles Theoretical Study of Formaldehyde Bonding on Rutile TiO₂(110)

Haubrich

Kaxiras

Friend

2011

Chemistry A European J

115

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We report a systematic investigation of the effects of different surface and subsurface point defects on the adsorption of formaldehyde on rutile TiO(2)(110) surfaces using density functional theory (DFT). All point defects investigated--including surface bridging oxygen vacancies, titanium interstitials, and subsurface oxygen vacancies--stabilize the adsorption significantly by up to 56 kJ mol(-1) at a coverage of 0.1 monolayer (ML). The stabilization is due to a decrease of the coordination (covalent saturation) of the surface Ti adsorption sites adjacent to the defects, which leads to a stronger molecule-surface interaction. This change in the Ti is caused by the removal of a neighboring atom (oxygen vacancies) or substantial lattice relaxations induced by the subsurface defects. On the stoichiometric reference surface, the most stable adsorption geometry of formaldehyde is a tilted η(2)-dioxymethylene (with an adsorption energy E(ads)=-125 kJ mol(-1)), in which a bond forms to a nearby bridging O atom and the carbonyl-O atom in the formaldehyde binds to a Ti atom in the adjacent fivefold coordinated lattice site. The η(1)-top configuration on five-coordinate Ti(4+) is much less favorable (E(ads)=-69 kJ mol(-1)). The largest stabilization is exerted by subsurface Ti interstitials between the first and second layers. These defects stabilize the η(2)-dioxymethylene structure by nearly 40 kJ mol(-1) to an adsorption energy of -164 kJ mol(-1). Contrary to popular belief, adsorption in a bridging oxygen vacancy (E(ads)=-86 kJ mol(-1)) is much less favorable for formaldehyde compared to the η(2)-dioxymethylene structures. From these results we conclude that formaldehyde will bind in the η(2)-dioxymethylene structure on the stoichiometric surface as well as in the presence of Ti interstitials and bridging oxygen vacancies. In the light of these substantial effects, we conclude that it is essential to include all the types of point defects present in typical, reduced rutile samples used for model studies, at realistic concentrations to obtain correct adsorption sites, structures, energetic, and chemi-physical properties.

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Section: Resultssupporting

confidence: 80%

The Role of Surface and Subsurface Point Defects for Chemical Model Studies on TiO₂: A First‐Principles Theoretical Study of Formaldehyde Bonding on Rutile TiO₂(110)

Haubrich

Kaxiras

Friend

2011

Chemistry A European J

115

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“…The above assignment is at variance with an earlier assignment of CpTiCl 3 by Basso-Bart et al [5]. Their assignment, based only on He(I) spectra and CNDO/2 calculations, must be contradicted.…”

Section: Cpticl 3 (Cp = C 5 H 5 C 5 H 4 Ch 3 C 5 (Ch 3 ) 5 )contrasting

confidence: 66%

“…Within the scope of our collaboration of η 5 -cyclopentadienyl complexes [4] we were interested in the bonding properties of a series of compounds CpMX 3 . One member of this series, CpTiCl 3 , has been studied before [5].…”

Section: Introductionmentioning

confidence: 99%

The He(I) and He(II) photoelectron spectra of some η5-cyclopentadienyl-titanium,-zirconium and -hafnium trihalide complexes

Terptra

Louwen

Oskam

et al. 1984

Journal of Organometallic Chemistry

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“…An early study of the He I and He II photoelectron spectrum of compound 1 concluded that there were 'striking similarities between the spectra of [TiMeCl 3 ] and TiCl 4 '. 10 In view of our experience regarding the difficulty in obtaining 1 rigorously pure (see Experimental section), suspicions must arise about the integrity of the sample in this earlier report. We, therefore, report below the photoelectron spectrum of an authentic sample of 1.…”

mentioning

confidence: 86%

Investigation of the bonding in methyl titanium trichloride by variable-energy photoelectron spectroscopy and density functional calculations

Field¹,

Green²,

Kaltsoyannis³

et al. 1997

J. Chem. Soc., Dalton Trans.

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Molecular orbitals and photoelectron spectra of some titanium(IV) organometallic compounds

Cited by 15 publications

References 26 publications

The Role of Surface and Subsurface Point Defects for Chemical Model Studies on TiO₂: A First‐Principles Theoretical Study of Formaldehyde Bonding on Rutile TiO₂(110)

The Role of Surface and Subsurface Point Defects for Chemical Model Studies on TiO₂: A First‐Principles Theoretical Study of Formaldehyde Bonding on Rutile TiO₂(110)

The He(I) and He(II) photoelectron spectra of some η5-cyclopentadienyl-titanium,-zirconium and -hafnium trihalide complexes

Investigation of the bonding in methyl titanium trichloride by variable-energy photoelectron spectroscopy and density functional calculations

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Molecular orbitals and photoelectron spectra of some titanium(IV) organometallic compounds

Cited by 15 publications

References 26 publications

The Role of Surface and Subsurface Point Defects for Chemical Model Studies on TiO2: A First‐Principles Theoretical Study of Formaldehyde Bonding on Rutile TiO2(110)

The Role of Surface and Subsurface Point Defects for Chemical Model Studies on TiO2: A First‐Principles Theoretical Study of Formaldehyde Bonding on Rutile TiO2(110)

The He(I) and He(II) photoelectron spectra of some η5-cyclopentadienyl-titanium,-zirconium and -hafnium trihalide complexes

Investigation of the bonding in methyl titanium trichloride by variable-energy photoelectron spectroscopy and density functional calculations

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The Role of Surface and Subsurface Point Defects for Chemical Model Studies on TiO₂: A First‐Principles Theoretical Study of Formaldehyde Bonding on Rutile TiO₂(110)

The Role of Surface and Subsurface Point Defects for Chemical Model Studies on TiO₂: A First‐Principles Theoretical Study of Formaldehyde Bonding on Rutile TiO₂(110)