Dissociation energies of the Ga2, In2, and GaIn molecules

Balducci, G.; Gigli, G.; Meloni, Giovanni

doi:10.1063/1.477041

Cited by 29 publications

(23 citation statements)

References 15 publications

(17 reference statements)

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“…Overall, the value calculated here is in reasonable agreement with the experimental value of 110.8 AE 4.9 kJ mol À1 . [22,23] The calculated relative energies of the electronic states of Ga 2 are in fair agreement with the results of earlier MR-ACPF calculations, [20] [20] GaH possesses a closed-shell ground state (…”

supporting

confidence: 84%

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: 84%

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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“…In addition, Himmel et al have characterized isolated Ga 2 dimers in an argon matrix with the aid of resonance Raman and UV/Vis spectroscopy [14]. Then, Balducci et al characterized the dissociation energies of Ga 2 cluster, which derived from the Knudsen cell-mass spectrometric [15]. …”

Section: Introductionmentioning

confidence: 99%

Geometrical Structures and Electronic Properties of Ga6 and Ga5X (X = B, C, N, O, F, Al, Si, P, S, Cl) Clusters

Yao

et al. 2018

Materials

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Based on the unbiased CALYPSO (Crystal structure Analysis by Particle Swarm Optimization) structure searching method in combination with density functional theory (DFT), the geometrical structures and electronic properties are investigated theoretically for Ga6 and Ga5X (X = B, C, N, O, F, Al, Si, P, S, Cl) clusters. The PBE0 exchange-correlation functional and the 6-311G(d) basis set is carried out to determine global minima on potential energy surfaces. The relative stabilities of the clusters are examined by the binding energies and substitution reaction. Following the predictions of the Jellium model, the Ga5B cluster with the 18 valence electrons is the most stable structure. At last, with the obtained lowest energy structures, some physical properties such as electrons transfer, molecular orbitals, and total and partial densities of states are discussed, respectively.

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“…Table I lists results for Al 2 , Ga 2 , and In 2 , for which the triplet state is the ground state for all three dimers; the exact ground state electron configuration has been under debate for a long time, with two candidates 3 u and 3 g − nearly degenerate. [60][61][62][63][64][65][66][67][68][69][70][71][72] Some recent experiments and calculations favor 3 u as the ground state. 62-65, 69, 70 Here we obtained a 3 g…”

Section: Numerical Detailsmentioning

confidence: 99%

Can orbital-free density functional theory simulate molecules?

Xia

Huang

Shin

et al. 2012

The Journal of Chemical Physics

104

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Orbital-free density functional theory (OFDFT), with its attractive linearly scaling computation cost and low prefactor, is one of the most powerful first principles methods for simulating large systems (~10(4)-10(6) atoms). However, approximating the electron kinetic energy with density functionals limits the accuracy and generality of OFDFT compared to Kohn-Sham density functional theory (KSDFT). In this work, we test whether the Huang-Carter (HC) kinetic energy density functional (KEDF), which contains the physics to properly describe covalently bonded semiconductor materials, can also be used to describe covalent bonds in molecules. In particular, we calculate a variety of homonuclear diatomic molecules with the HC functional within OFDFT. The OFDFT bond dissociation energy, equilibrium bond length, and vibrational frequency of these dimers are in remarkably good agreement with benchmark KSDFT results, given the lack of orbitals in the calculation. We vary the two parameters λ (controlling the reduced density gradient contribution to the nonlocal kernel) and β (the exponent of the density in the nonlocal term) present in the HC KEDF and find that the optimal λ correlates with the magnitude of the highest occupied molecular orbital-lowest unoccupied molecular orbital energy gap. Although the HC KEDF represents a significant improvement over previous KEDFs in describing covalent systems, deficiencies still exist. Despite the similar overall shape of the KSDFT and OFDFT ground state electron densities, the electron density within the bonding region is still quite different. Furthermore, OFDFT is not yet able to give reasonable description of magnetic states. The energy orderings of the triplet and singlet states of Si(2) and Al family dimers are not consistent with KSDFT or experimental results and the spin polarization distributions also differ widely between the two theories.

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Dissociation energies of the Ga2, In2, and GaIn molecules

Cited by 29 publications

References 15 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

Geometrical Structures and Electronic Properties of Ga6 and Ga5X (X = B, C, N, O, F, Al, Si, P, S, Cl) Clusters

Can orbital-free density functional theory simulate molecules?

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Dissociation energies of the Ga2, In2, and GaIn molecules

Cited by 29 publications

References 15 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

Geometrical Structures and Electronic Properties of Ga6 and Ga5X (X = B, C, N, O, F, Al, Si, P, S, Cl) Clusters

Can orbital-free density functional theory simulate molecules?

Contact Info

Product

Resources

About

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