Theoretical study of Si3H3+ and Ge3H3+ isomers

So, Suk Ping

doi:10.1016/s0009-2614(99)01089-1

Cited by 11 publications

(8 citation statements)

References 24 publications

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“…The Si 3 Au 3 + cation is interesting because its hydride analog, the cyclotrisilenylium ion (D 3h Si 3 H 3 + ) is a 2p aromatic species, which has been extensively studied. [60][61][62][63][64] An aromatic cyclotrisilenylium ion with bulky substituents, which bears similarities with Si 3 H 3 + , has been successfully synthesized. 65 Our structural search indeed showed that the lowest energy isomer for Si 3 Au 3 + (D 3h , 1 A 1 ) is identical to Si 3 H 3 + .…”

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confidence: 99%

Covalent gold

Wang

2010

Phys. Chem. Chem. Phys.

110

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Gold is known to be the noblest of all metals because of the relativistic stabilization of its outer 6s orbital. The relativistic effects also lead to destabilization of the 5d orbitals, reducing the 6s-5d energy gap and enhancing s-d hybridization. Therefore, in contrast to its lighter congeners, gold exhibits significant covalent bonding characters and a remarkable repertoire of chemistry, which are increasingly being exploited in catalysis and nanotechnology. This Perspective presents a brief account of recent experimental efforts in the author's laboratory using photoelectron spectroscopy that lead to direct observations of covalent bonding in several relatively simple Au compounds: Au oxides (AuO(-) and AuO(2)(-)), sulfides (AuS(-) and AuS(2)(-)), and the well-known Au(CN)(2)(-) complex. In a series of Au-Si and Au-B mixed clusters, it has also been found that gold atoms behave like H atoms, forming auro-silicon and auro-boron clusters with strong covalent bonding, analogous to the corresponding silicon and boron hydrides, such as the tetrahedral auro-silane (SiAu(4)) versus silane (SiH(4)).

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confidence: 99%

Covalent gold

Wang

2010

Phys. Chem. Chem. Phys.

110

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“…15 The various basis sets for G2 calculations of compounds containing third-row elements have been developed by Curtiss et al [16][17][18] and shown to give energy results with an average absolute deviation of 1.37 kcal mol -1 from experiment for 40 test reactions.…”

Section: Calculationsmentioning

confidence: 99%

“…single-point energy calculations because correlating these orbitals has been found to be important in the calculations of Ge 3 H 3 + isomers. 15 The various basis sets for G2 calculations of compounds containing third-row elements have been developed by Curtiss et al [16][17][18] and shown to give energy results with an average absolute deviation of 1.37 kcal mol -1 from experiment for 40 test reactions.…”

Section: Calculationsmentioning

confidence: 99%

Ab Initio Molecular Orbital Study of the Reaction of GeH₂ with H₂O and Decomposition Reactions of H₃GeOH

2001

J. Phys. Chem. A

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The formation of H 3 GeOH from GeH 2 and H 2 O and its decomposition paths have been studied using the G2 molecular orbital method. It is predicted that GeH 2 reacts with H 2 O exothermically (by 10.0 kcal mol -1 ) without a barrier to form a nonplanar complex, H 2 GeOH 2 , which isomerizes via a 1,2-H shift to H 3 GeOH with a barrier of 28.3 kcal mol -1 . The backward isomerization requires an activation energy of 61.1 kcal mol -1 . In addition, direct decompositions of H 3 GeOH yielding H 3 GeO + H, H 3 Ge + OH, and H 2 GeOH + H are shown to have large endothermicities of 113.7, 102.4, and 84.9 kcal mol -1 , and those producing H 2 -GeO + H 2 and HGeOH + H 2 to have activation energies of 82.1 and 57.6 kcal mol -1 , respectively. Hence, H 3 GeOH is stable to the above decomposition processes unless its temperature is moderately high or above.

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“…They measured the rate constants for second‐ and third‐order reactions of all the primary ions GeH n + ( n = 0–3) and observed secondary ions up to Ge 2 H 7 + and Ge 3 H 9 + . Many experimental2–5 and theoretical6–17 studies on the structure, stability, and thermochemistry of GeH n + ( n ≥ 1) and Ge m H n + ( m > 1, n ≥ 1) have been also subsequently reported. Over the years, the interest in the chemistry of ionised GeH 4 and GeH 4 ‐based mixtures has become progressively related to the preparation, by chemical vapour deposition techniques,18 of amorphous semiconductors for electronic and optoelectronic devices 19, 20.…”

Section: Introductionmentioning

confidence: 99%

Ion chemistry in germane/fluorocompounds gaseous mixtures: a mass spectrometric and theoretical study

et al. 2008

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The ion-molecule reactions occurring in GeH(4)/NF(3), GeH(4)/SF(6), and GeH(4)/SiF(4) gaseous mixtures have been investigated by ion trap mass spectrometry and ab initio calculations. While the NF(x)(+) (x=1-3) react with GeH(4) mainly by the exothermic charge transfer, the open-shell Ge(+) and GeH(2)(+) undergo the efficient F-atom abstraction from NF(3) and form GeF(+) and F-GeH(2)(+) as the only ionic products. The mechanisms of these two processes are quite similar and involve the formation of the fluorine-coordinated complexes Ge-F-NF(2)(+) and H(2)Ge-F-NF(2)(+), their subsequent crossing to the significantly more stable isomers FGe-NF(2)(+) and F-GeH(2)-NF(2)(+), and the eventual dissociation of these ions into GeF(+) (or F-GeH(2)(+)) and NF(2). The closed-shell GeH(+) and GeH(3)(+) are instead much less reactive towards NF(3), and the only observed process is the less efficient formation of GeF(+) from GeH(+). The theoretical investigation of this unusual H/F exchange reaction suggests the involvement of vibrationally-hot GeH(+). Passing from NF(3) to SF(6) and SiF(4), the average strength of the M-F bond increases from 70 to 79 and 142 kcal mol(-1), and in fact the only process observed by reacting GeH(n)(+) (n=0-3) with SF(6) and SiF(4) is the little efficient F-atom abstraction from SF(6) by Ge(+). Irrespective of the experimental conditions, we did not observe any ionic product of Ge-N, Ge-S, or Ge-Si connectivity. This is in line with the previously observed exclusive formation of GeF(+) from the reaction between Ge(+) and C-F compounds such as CH(3)F. Additionally observed processes include in particular the conceivable formation of the elusive thiohypofluorous acid FSH from the reaction between SF(+) and GeH(4).

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Theoretical study of Si3H3+ and Ge3H3+ isomers

Cited by 11 publications

References 24 publications

Covalent gold

Covalent gold

Ab Initio Molecular Orbital Study of the Reaction of GeH₂ with H₂O and Decomposition Reactions of H₃GeOH

Ion chemistry in germane/fluorocompounds gaseous mixtures: a mass spectrometric and theoretical study

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Theoretical study of Si3H3+ and Ge3H3+ isomers

Cited by 11 publications

References 24 publications

Covalent gold

Covalent gold

Ab Initio Molecular Orbital Study of the Reaction of GeH2 with H2O and Decomposition Reactions of H3GeOH

Ion chemistry in germane/fluorocompounds gaseous mixtures: a mass spectrometric and theoretical study

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Ab Initio Molecular Orbital Study of the Reaction of GeH₂ with H₂O and Decomposition Reactions of H₃GeOH