Chapter 10. THE ELUSIVE SiO BOND

Gibbs, G. V.; Downs, James W.; Boisen, M. B.

doi:10.1515/9781501509698-015

Cited by 36 publications

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“…However, when regarding energetic contributions to the bonding these bonds are favored by an orbital stabilization. As mentioned in the Introduction, the Si−O bond was termed the “elusive” bond by Gibbs et al …”

Section: Resultsmentioning

confidence: 99%

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A Variety of Bond Analysis Methods, One Answer? An Investigation of the Element−Oxygen Bond of Hydroxides H_nXOH

Fugel

Beckmann

Jayatilaka

et al. 2018

Chemistry A European J

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There is a great variety of bond analysis tools that aim to extract information on the bonding situation from the molecular wavefunction. Because none of these can fully describe bonding in all of its complexity, it is necessary to regard a balanced selection of complementary analysis methods to obtain a reliable chemical conclusion. This is, however, not a feasible approach in most studies because it is a time-consuming procedure. Therefore, we provide the first comprehensive comparison of modern bonding analysis methods to reveal their informative value. The element-oxygen bond of neutral H XOH model compounds (X=Li, Be, B, C, N, O, F, Na, Mg, Al, Si, P, S, Cl) is investigated with a selection of different bond analysis tools, which may be assigned into three different categories: i) real space bonding indicators (quantum theory of atoms in molecules (QTAIM), the electron localizability indicator (ELI-D), and the Raub-Jansen index), ii) orbital-based descriptors (natural bond orbitals (NBO), natural resonance theory (NRT), and valence bond (VB) calculations), and iii) energy analysis methods (energy decomposition analysis (EDA) and the Q-analysis). Besides gaining a deep insight into the nature of the element-oxygen bond across the periodic table, this systematic investigation allows us to get an impression on how well these tools complement each other. Ionic, highly polarized, polarized covalent, and charge-shift bonds are discerned from each other.

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Section: Resultsmentioning

confidence: 99%

“…Gibbs et al. regard the Si−O bond as a mixture of both—they call it the “elusive” bond . The Si−O bond in siloxane systems (i.e., R‐Si‐O‐Si‐R′) was investigated in terms of the experimental and theoretical electron density by Grabowsky et al., who confirmed the ionic nature of the Si−O bond.…”

Section: Introductionmentioning

confidence: 99%

A Variety of Bond Analysis Methods, One Answer? An Investigation of the Element−Oxygen Bond of Hydroxides H_nXOH

Fugel

Beckmann

Jayatilaka

et al. 2018

Chemistry A European J

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“…A later calculation by Nicholas et al [34] contributed to this conclusion, by finding that the ionicity of the bond increases by ∼ 25% if the Si-O-Si angle widens from 130 ° to 180 ° and the Si-O shortens. In general, the force field that governs the Si-O bond length and the related Si-O-Si angle, as well as their respective stretching and bending, can be seen as independent from the long-range forces of an entire crystal [35] . Therefore, the sequence of the phase transitions and symmetry breakdowns in coesite under pressure is most likely controlled by highly compressible S1 tetrahedron and, in particular, by its most compressible Si1-O1 bond.…”

Section: Resultsmentioning

confidence: 99%

High-pressure crystal chemistry of coesite-I and its transition to coesite-II

Černok

Bykova

Ballaran

et al. 2014

Zeitschrift Für Kristallographie - Crystalline Materials

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The high-pressure crystal chemistry of coesite was studied by means of single crystal X-ray diffraction in the pressure interval ∼ 2 -34 GPa and at ambient temperature. We compressed the samples using diamond-anvil cells loaded with neon as pressure-transmitting medium and collected X-ray diffraction data using synchrotron radiation. The thermodynamically stable coesite -coesite-I -was observed up to ∼ 20 GPa, with the following unit-cell parameters: a = 6.6533(12) Å , b = 11.9018(10) Å , c = 6.9336(10) Å , β = 121.250(20) ° and V = 469.38(15) Å 3 . The volume-pressure data of coesite-I are described by means of a third-order Birch-Murnhagan EoS with parameters V 0 = 547.26(66) Å 3 ,. Above such pressure we witness the formation of a well crystallized coesite-II, previously observed only by spectroscopic studies. The structure of the novel high-P polymorph was determined and refined at ∼ 28 and ∼ 31 GPa with final R indices of 8% and 12%, respectively. Coesite-II has P 2 1 /n symmetry and a unit cell that is " doubled " along the b -axis with respect to that of the initial coesite-I: a = 6.5591(10) Å , b = 23.2276(14) Å , c = 6.7953(9) Å , β = 121.062(19) ° and V = 886.84(19) Å 3 at ∼ 28 GPa. All Si atoms are in tetrahedral coordination. The displacive phase transition I-> II is likely driven by the extreme shortening (0.05 Å or 3.2%) of the shortest and the most compressible Si1-O1 bond, related to the stiff 180 ° Si1-O1-Si1 angle. Under compression the linear angle bends, resulting in two independent angles, one of which, however, retains almost linear geometry ( ∼ 178 ° ). The requirement of this angle to be close to linear likely causes further Si-O compression down to an extremely short distance of ∼ 1.52 Å which prompts subsequent structural changes, with the formation of a triclinic phase at ∼ 31 GPa, coesite-III.

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“…Instead we compare the Si-O and Ge-O bond distances (Shannon and Prewitt 1969). The geometry of the Si(OH) 4 molecule given by Gibbs et al (1994) suggests that these bond lengths should closely approximate the molecular radius. The Si-O distance is 160.7 pm, while Ge-O is 173.8 pm.…”

Section: Passive Vs Active Mechanisms Of Ge-si Fractionationmentioning

confidence: 99%

Subcellular localization of silicon and germanium in grass root and leaf tissues by SIMS: evidence for differential and active transport

et al. 2010

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Silicon transport and incorporation into plant tissue is important to both plant physiological function and to the influence plants have on ecosystem silica cycling. However, the mechanisms controlling this transport have only begun to be explored. In this study, we used secondary ion mass spectrometry (SIMS) to image concentrations of Si in root and shoot tissues of annual blue grass (Poa annua L.) and orchard grass (Dactylis glomerata L.) with the goal of identifying control points in the plant silica uptake pathway. In addition, we used SIMS to describe the distributions of germanium (Ge); the element used to trace Si in biogeochemical studies. Within root tissue, Si and Ge were localized in the suberized thickwalled region of endodermal cells, i.e. the proximal side of endodermal cells which is in close association to the casparian strip. In leaves, Si was present in the cell walls, but Ge was barely detectable. The selective localization of Si and Ge in the proximal side of endodermal cell walls of roots suggests transport control is exerted upon Si and Ge by the plant. The absence of Si in most root cell walls and its presence in the cell walls of leaves (in areas outside of the transpiration terminus) suggests modifications in the chemical form of Si to a form that favors Si complexation in the cell walls of leaf tissue. The low abundance of Ge in leaf tissue is consistent with previous studies that suggest preferential transport of Si relative to Ge.

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Chapter 10. THE ELUSIVE SiO BOND

Cited by 36 publications

References 0 publications

A Variety of Bond Analysis Methods, One Answer? An Investigation of the Element−Oxygen Bond of Hydroxides H_nXOH

A Variety of Bond Analysis Methods, One Answer? An Investigation of the Element−Oxygen Bond of Hydroxides H_nXOH

High-pressure crystal chemistry of coesite-I and its transition to coesite-II

Subcellular localization of silicon and germanium in grass root and leaf tissues by SIMS: evidence for differential and active transport

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Chapter 10. THE ELUSIVE SiO BOND

Cited by 36 publications

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A Variety of Bond Analysis Methods, One Answer? An Investigation of the Element−Oxygen Bond of Hydroxides HnXOH

A Variety of Bond Analysis Methods, One Answer? An Investigation of the Element−Oxygen Bond of Hydroxides HnXOH

High-pressure crystal chemistry of coesite-I and its transition to coesite-II

Subcellular localization of silicon and germanium in grass root and leaf tissues by SIMS: evidence for differential and active transport

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A Variety of Bond Analysis Methods, One Answer? An Investigation of the Element−Oxygen Bond of Hydroxides H_nXOH

A Variety of Bond Analysis Methods, One Answer? An Investigation of the Element−Oxygen Bond of Hydroxides H_nXOH