Aluminium, gallium and indium dihydrides. An IR matrix isolation and ab initio study

Pullumbi, Pluton; Mijoule, C.; Manceron, L.; Bouteiller, Y.

doi:10.1016/0301-0104(94)00110-3

Cited by 76 publications

(149 citation statements)

References 27 publications

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“…[4,5] The experimental results clearly show that GaH 2 is a bent molecule with C 2v symmetry. On the basis of the experimental results, the H-Ga-H bond angle was estimated to be approximately 1208.…”

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confidence: 91%

“…Ga atoms instead require photoactivation through (2)]. [4,5] However, both reactions are exothermic. Thus, a Ga atom carrying an unpaired electron in one of the frontier 4p orbitals, which one might intuitively expect to be more reactive than a Ga 2 dimer, turns out to be relatively inert.…”

Section: Introductionmentioning

confidence: 99%

“…The bond length and the harmonic vibrational frequency are predicted to be 1.65 ä and 1668 cm . [4,24] It is evident from the values calculated with different methods and basis sets (see Table 1) that dynamic correlation and d-shell inclusion lead to further significant alterations in the values calculated for these observable parameters.…”

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confidence: 95%

“…[3,4] It follows that each reaction involves a one-step process for which a choice of reaction coordinates is indicated in Figure 2. In addition, extremely useful experimental information for the reaction of Ga 2 with H 2 is to hand.…”

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confidence: 99%

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Why Does a Ga₂ Dimer React Spontaneously with H₂, but a Ga Atom Does Not?—A Detailed Quantum Chemical Investigation of the Differences in Reactivity Between Ga Atoms and Ga₂ Dimers, in Combination with Experimental Results

Köhn

Himmel

Gaertner

2003

Chemistry A European J

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The spontaneous and photoactivated reactions between Ga(2) and H(2) in a matrix of solid Ar at 12 K have been followed by using IR spectroscopy and have been shown to give access to several isomers of the subvalent hydride Ga(2)H(2). We now present Raman spectra for this system, to complete its characterization on the basis of vibrational spectra. In addition, the differences between the reactivity of a Ga atom and a Ga(2) dimer toward H(2) are evaluated. The matrix isolation experiments have shown that Ga(2) reacts spontaneously with H(2,) at 12 K, to give the cyclic subvalent hydride Ga(micro-H)(2)Ga (D(2h) symmetry), which can be transformed into two other isomers of Ga(2)H(2) by selective photoactivation. Interestingly, the spontaneous reaction is subject to a marked isotopic effect. In total, the experimental results provide detailed information about the reaction mechanism. In contrast to Ga(2), Ga atoms do not react spontaneously with H(2); on photoactivation they instead yield the radical species GaH(2). The quantum chemical calculations presented herein start with an analysis of the structures and relative energies of the relevant species at the MP2 level, by using extended basis sets, and lead on to a discussion of the correlation diagrams for both reactions. Finally, CASSCF and MRCI methods, in combination with moderate-sized basis sets, were employed to analyze in detail the mechanisms of the two reactions. It will be shown that the computational results, in concert with the experimental findings, provide a satisfying explanation of the contrasting reactivities of Ga and Ga(2).

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confidence: 91%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 95%

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confidence: 99%

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Why Does a Ga₂ Dimer React Spontaneously with H₂, but a Ga Atom Does Not?—A Detailed Quantum Chemical Investigation of the Differences in Reactivity Between Ga Atoms and Ga₂ Dimers, in Combination with Experimental Results

Köhn

Himmel

Gaertner

2003

Chemistry A European J

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“…Analogous experiments with D 2 give the spectra shown in Figure 2. À1 ,respectively, which are between the gas phase (1424.8 and 1023.5 cm À1 ) [10][11][12] and solid argon (1387.4 and 995.9 cm À1 ) [13] fundamentals for InH and InD, respectively. The weaker 1628.9/1563.3 cm À1 and 1175.4/ 1126.3 cm À1 band pairs are assigned to InH 2 and InD 2 , respectively, as these bands are 13-15 cm À1 higher the corresponding bands documented in argon matrix.…”

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confidence: 99%

Infrared Spectra of Indium Hydrides in Solid Hydrogen and of Solid Indane

Andrews

Wang

2004

Angew Chem Int Ed

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One little indium: Reactions of laser‐ablated indium atoms with pure hydrogen give sharp IR absorptions corresponding to InH intermediate species. Irradiation at 193 nm maximizes further reaction to give the indane monomer InH3. Annealing provides evidence for In2H6 and ultimately the sharp absorption bands are replaced with a broad IR band centered at 1460 cm−1 assigned to solid indane (InH3)n [see Equation].${\vcenter{\openup.5em\halign{$#$\cr {\rm InH}_{3}\rightarrow {1\over 2}{\rm In}_{2}{\rm H}_{6}\rightarrow {1\over n}({\rm InH}_{3})_{n}\hfill\cr}}}$

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Charakterisierung und Photochemie der Gallium- und Indiumsubhydride Ga2H2 und In2H2

et al. 2002

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In dieser Arbeit beschreiben wir die Cokondensation von Ga-oder In-Dampf mit H 2 in Ar im ‹berschuss bei 10 ± 12 K und die nachfolgende Bestrahlung der erzeugten Matrix mit Licht unterschiedlicher Wellenl‰ngen. Wir zeigen, dass sich durch Umsetzung von Ga 2 oder In 2 mit H 2 direkt oder indirekt drei Ga 2 H 2 -Isomere und zwei In 2 H 2 -Isomere bilden: 1) die Bis(m-hydrido)-Spezies Ga(m-H) 2 Ga 1 a und In(m-H) 2 In 1 b, 2) die trans-gewinkelten Spezies HGaGaH 3 a und HInInH 3 b und 3) GaGaH 2 2 a mit zwei terminalen Ga-H-Bindungen (Schema 1). S‰mtliche Verbindungen wurden IR-spektroskopisch und durch einen Vergleich von gemessenen mit quantenchemisch berechneten Spektren sowie mit Spektren bereits bekannter Gallium-und Indiumhydridverbindungen identifiziert und charakterisiert. Die Untersuchungen ergaben, dass sich die Isomere durch selektive Photolyse ineinander umwandeln lassen.Die Subhydride der 13. Gruppe sind nicht nur wegen des mˆglichen Auftretens von Metall-Metall-Wechselwirkungen in M(m-H) 2 M-Spezies und von Mehrfachbindungen in HMMH-Spezies (M Ga, In) von Interesse, sondern auch wegen ihrer Bedeutung als Vorstufen oder Intermediate bei der chemischen Gasphasenabscheidung (CVD) zur Herstellung neuer metallischer oder Halbleitermaterialien. Die Verbindungen wurden zwar bereits in mehreren theoretischen Arbeiten beschrieben, [1±4] experimentelle Befunde liegen aber nur f¸r lineares HBBH [5] und f¸r Al(m-H) 2 Al [6] vor, die in Matrix identifiziert werden konnten. aehnliche Experimente mit thermisch verdampftem Gallium lassen vermuten, [7] dass Ga 2 spontan mit H 2 zu 1 a reagiert, das wie Al(m-H) 2 Al das planare Strukturmotiv A aufweisen sollte. Von den anderen M 2 H 2 -Isomeren (mˆgliche Strukturmotive B ± D) wurde lediglich HAl(m-H)Al mit dem nicht gesicherten Strukturmotiv D identifiziert. [6] Schema 1. Thermisch und photolytisch induzierte Matrixreaktionen von a) Ga 2 und H 2 und b) In 2 und H 2 .

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Aluminium, gallium and indium dihydrides. An IR matrix isolation and ab initio study

Cited by 76 publications

References 27 publications

Why Does a Ga₂ Dimer React Spontaneously with H₂, but a Ga Atom Does Not?—A Detailed Quantum Chemical Investigation of the Differences in Reactivity Between Ga Atoms and Ga₂ Dimers, in Combination with Experimental Results

Why Does a Ga₂ Dimer React Spontaneously with H₂, but a Ga Atom Does Not?—A Detailed Quantum Chemical Investigation of the Differences in Reactivity Between Ga Atoms and Ga₂ Dimers, in Combination with Experimental Results

Infrared Spectra of Indium Hydrides in Solid Hydrogen and of Solid Indane

Charakterisierung und Photochemie der Gallium- und Indiumsubhydride Ga2H2 und In2H2

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Aluminium, gallium and indium dihydrides. An IR matrix isolation and ab initio study

Cited by 76 publications

References 27 publications

Why Does a Ga2 Dimer React Spontaneously with H2, but a Ga Atom Does Not?—A Detailed Quantum Chemical Investigation of the Differences in Reactivity Between Ga Atoms and Ga2 Dimers, in Combination with Experimental Results

Why Does a Ga2 Dimer React Spontaneously with H2, but a Ga Atom Does Not?—A Detailed Quantum Chemical Investigation of the Differences in Reactivity Between Ga Atoms and Ga2 Dimers, in Combination with Experimental Results

Infrared Spectra of Indium Hydrides in Solid Hydrogen and of Solid Indane

Charakterisierung und Photochemie der Gallium- und Indiumsubhydride Ga2H2 und In2H2

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Why Does a Ga₂ Dimer React Spontaneously with H₂, but a Ga Atom Does Not?—A Detailed Quantum Chemical Investigation of the Differences in Reactivity Between Ga Atoms and Ga₂ Dimers, in Combination with Experimental Results

Why Does a Ga₂ Dimer React Spontaneously with H₂, but a Ga Atom Does Not?—A Detailed Quantum Chemical Investigation of the Differences in Reactivity Between Ga Atoms and Ga₂ Dimers, in Combination with Experimental Results