Chemisorption of HSi(OH)3 on silica surfaces: an ab initio periodic study

Baraille, Isabelle; Loudet, Michel; Lacombe, Sylvie; Cardy, H.; Pisani, Cesare

doi:10.1016/s0166-1280(02)00609-7

Cited by 10 publications

(9 citation statements)

References 24 publications

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“…Some examples of its usage are cited to illustrate its capabilities. 131,381,382 The tutorial article 380 by the authors of CRYSTAL is an excellent introduction to solid-state calculations in chemistry. Whereas CRYSTAL, Quantum Espresso, and VASP support hybrid calculations, most solid-state codes do not support nonlocal functionals.…”

Section: Softwarementioning

confidence: 99%

Density functional theory for transition metals and transition metal chemistry

Cramer

Truhlar

2009

Phys. Chem. Chem. Phys.

1,531

1,342

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We introduce density functional theory and review recent progress in its application to transition metal chemistry. Topics covered include local, meta, hybrid, hybrid meta, and range-separated functionals, band theory, software, validation tests, and applications to spin states, magnetic exchange coupling, spectra, structure, reactivity, and catalysis, including molecules, clusters, nanoparticles, surfaces, and solids.

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Section: Softwarementioning

confidence: 99%

Density functional theory for transition metals and transition metal chemistry

Cramer

Truhlar

2009

Phys. Chem. Chem. Phys.

1,531

1,342

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“…It has been shown in previous work [12,14,15] that periodic edingtonite, a natural zeolite, is a good model for amorphous silica surfaces. Surfaces with different types of hydroxyl groups are easily obtained by cutting the edingtonite bulk along different crystallographic planes and saturating the dangling bonds with H atoms.…”

Section: Model Structuresmentioning

confidence: 99%

“…We consider OH in different environments, spanning semi-ionic metal hydroxides like brucite (crystalline Mg(OH) 2 ) and portlandite (Ca(OH) 2 ) to the hydroxylated (001) face of edingtonite, which has been shown [12,14,15] to mimic the spectral features of amorphous silica surfaces outgassed at 400 K, and as a typical zeolite acidic chabazite. In all cases anharmonicity is responsible for a remarkable shift in the OH stretching frequency, of the order of 150-180 cm À1 .…”

Section: Introductionmentioning

confidence: 99%

Quantum mechanical calculation of the OH vibrational frequency in crystalline solids

Tosoni

Pascale²,

Ugliengo

et al. 2005

Molecular Physics

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The OH vibrational frequency of four crystalline compounds ranging from ionic (brucite, Mg(OH) 2 , and portlandite, Ca(OH) 2 ) to semi-covalent (edingtonite, as representative of free surface OH groups in silica, and acid chabazite, as representative of acid zeolites) has been investigated at quantum mechanical level with the CRYSTAL program using the B3LYP hybrid functional. The OH vibration is calculated in two ways: (i) in the harmonic approximation, by diagonalizing the fully coupled dynamical matrix to yield the harmonic frequency ! h . (ii) at the anharmonic level, by decoupling the OH stretching mode from the bulk phonons and by numerically solving the one-dimensional Schro¨dinger equation associated with the OH potential energy to yield the fundamental ! 01 and the first overtone ! 02 frequencies. The harmonic and anharmonic frequencies differ by more than 150 cm À1 . In the cases where direct comparison is possible (brucite, portlandite and edingtonite), the experimental and calculated frequencies differ by less than 10 cm À1 ; the calculated anharmonicity constant, ! e x e ¼ (2! 01 À ! 02 )/2, is systematically smaller than the experimental value by about 10 cm À1 . The effect of the computational parameters on the computed frequencies is explored, with particular attention to the grid used for the construction of the DFT exchange and correlation contribution to the Hamiltonian and the accuracy in the geometry optimisation.

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“…The silica surface has been modeled by cristobalite (C (110) ), [21][22][23][24] and edingtonite (E (100) ), [25][26][27] which are both represented in Fig. 1.…”

Section: Modelsmentioning

confidence: 99%

“…In the particular case of amorphous silica, the periodic models are constructed from an ideal polymorph of SiO 2 , in particular a-quartz, 20 b-cristobalite [20][21][22][23][24] and edingtonite. [25][26][27][28] Transition metal based catalysts on silica surfaces have been modeled using finite clusters [29][30][31][32][33][34][35][36][37][38][39][40][41][42] and CPMD calculations have been carried out for a silica supported zirconium hydride. 22 In this work, we have carried out DFT periodic calculations of the experimental organometallic silica grafted complexes including the real set of ligands.…”

Section: Introductionmentioning

confidence: 99%

Structure, spectroscopic and electronic properties of a well defined silica supported olefin metathesis catalyst, [(SiO)Re(CR)(CHR)(CH₂R)], through DFT periodic calculations: silica is just a large siloxy ligand

et al. 2006

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DFT plane-wave periodic calculations using the VASP code have been carried out to model the silica supported olefin metathesis catalyst, [(RSiO)Re(RCR)(QCHR)(CH 2 R)]. The structure, spectroscopic and electronic properties of this highly active catalyst have been compared with those of non-efficient molecular analogues, [(X 3 SiO)Re(RCR)(QCHR)(CH 2 R)] (X 3 SiO is triphenylsiloxy or polyoligomeric silsesquioxane (POSS)). The silica surface was modelled using cristobalite and edingtonite ideal polymorph surfaces, and the organometallic fragment has been represented with the experimental (R = tBu) and simplified (R = Me) ligands, [(RSiO)Re(RCR)(QCHR)(CH 2 R)]. The calculated structures, alkylidene J C-H coupling constants and n C-H stretching frequencies agree with experimental data. The syn and anti isomers of the Re complexes are close in energy, the former being always more stable. A secondary ReÁ Á ÁO interaction experimentally detected by EXAFS is found to have no stabilizing influence, but is possible because of the facile distortion of (RSiO)Re(RCR)(QCHR)(CH 2 R). More importantly, the geometry and electronic structure of the Re fragment is essentially the same for the triphenylsiloxy, the POSS and the silica surface, which shows that the siloxy group of the first coordination sphere of Re determines the metal properties. The silica surface is thus electronically equivalent to the other siloxy groups, and should be viewed as a large bulky ligand.

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Chemisorption of HSi(OH)3 on silica surfaces: an ab initio periodic study

Cited by 10 publications

References 24 publications

Density functional theory for transition metals and transition metal chemistry

Density functional theory for transition metals and transition metal chemistry

Quantum mechanical calculation of the OH vibrational frequency in crystalline solids

Structure, spectroscopic and electronic properties of a well defined silica supported olefin metathesis catalyst, [(SiO)Re(CR)(CHR)(CH₂R)], through DFT periodic calculations: silica is just a large siloxy ligand

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Chemisorption of HSi(OH)3 on silica surfaces: an ab initio periodic study

Cited by 10 publications

References 24 publications

Density functional theory for transition metals and transition metal chemistry

Density functional theory for transition metals and transition metal chemistry

Quantum mechanical calculation of the OH vibrational frequency in crystalline solids

Structure, spectroscopic and electronic properties of a well defined silica supported olefin metathesis catalyst, [(SiO)Re(CR)(CHR)(CH2R)], through DFT periodic calculations: silica is just a large siloxy ligand

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Structure, spectroscopic and electronic properties of a well defined silica supported olefin metathesis catalyst, [(SiO)Re(CR)(CHR)(CH₂R)], through DFT periodic calculations: silica is just a large siloxy ligand