Stability and structure of Li<i>n</i>H molecules (<i>n</i>=3–6): Experimental and density functional study

Wu, C.H.; Jones, R.

doi:10.1063/1.1648305

Cited by 15 publications

(5 citation statements)

References 23 publications

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“…Interatomic distances inside Li 3 H moieties are summarized in Table 1. Both pyramidal and T-shaped Li 3 H moieties in TSs have structures similar the two isomers of isolated Li 3 H cluster, 31 found in a previous theoretical study. For example, in free pyramidal Li 3 H cluster, calculated at the same level of theory, Li−H distances are 1.89, 1.89, and 1.90 Å, a little longer than in TS11 and all Li−Li distances are 2.61 Å, a little shorter than in TS11.…”

Section: ■ Results and Discussionsupporting

confidence: 80%

Mechanisms of Hydrogen Generation from Tetrameric Clusters of Lithium Amidoborane

2015

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The first-principles study of dehydrogenation mechanism of tetrameric clusters of lithium amidoborane LiNH2BH3, (LiAB)4, is presented. The choice of tetramer is based on the suspicion that dimeric cluster models used in previous theoretical studies are too small to capture the essence of the reaction. Dehydrogenation pathways starting from three isomers of (LiAB)4 tetramers were explored by applying the artificial force induced reaction (AFIR) method at the M06 level of theory. All obtained reaction pathways feature initial dimerization of two LiAB molecules in the tetramer. Formation of intermediates containing the Li3H moiety is a very characteristic feature of all pathways. In the succeeding rate-limiting step of the release of H2 molecule, a hydridic H atom of the Li3H moiety activates a protic H atom of the NH2 group with formation of the Li2H2 moiety in transition state. The most kinetically favorable pathway has the activation enthalpy of 26.6 kcal mol(-1), substantially lower than that found for dimeric cluster. The obtained results suggest that only three LiAB molecules directly participate in the elementary reactions.

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Section: ■ Results and Discussionsupporting

confidence: 80%

Mechanisms of Hydrogen Generation from Tetrameric Clusters of Lithium Amidoborane

2015

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“…For comparison, the IE values of bare Li n [44] and Li n H [45] are also presented in the same table.…”

Section: Resultsmentioning

confidence: 98%

“…The values of the ionization energies of Li n Cl (n = 2–6) obtained in the present experiment are shown in Table . For comparison, the IE values of bare Li n and Li n H are also presented in the same table.…”

Section: Resultsmentioning

confidence: 99%

Formation and ionization energies of small chlorine‐doped lithium clusters by thermal ionization mass spectrometry

Veličković

Djustebek

Veljković

et al. 2012

Rapid Comm Mass Spectrometry

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“…Lithium hydride anions have been investigated in the gas phase by photoelectron spectroscopy . The small Li n H molecules have been identified in mass spectrometric measurements, and their stability and structure have been studied with density functional and large coupled-cluster computations. , …”

Section: Introductionmentioning

confidence: 99%

Infrared Spectra and Theoretical Calculations of Lithium Hydride Clusters in Solid Hydrogen, Neon, and Argon

Wang

Andrews

2007

J. Phys. Chem. A

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A matrix isolation IR study of laser-ablated lithium atom reactions with H2 has been performed in solid para-hydrogen, normal hydrogen, neon, and argon. The LiH molecule and (LiH)(2,3,4) clusters were identified by IR spectra with isotopic substitution (HD, D(2), and H(2) + D(2)) and comparison to frequencies calculated by density functional theory and the MP2 method. The LiH diatomic molecule is highly polarized and associates additional H(2) to form primary (H(2))(2)LiH chemical complexes surrounded by a physical cage of solid hydrogen where the ortho and para spin states form three different primary complexes and play a role in the identification of the bis-dihydrogen complex and in characterization of the matrix cage. The highly ionic rhombic (LiH)(2) dimer, which is trapped in solid matrices, is calculated to be 22 kcal/mol more stable than the inverse hydrogen bonded linear LiH-LiH dimer, which is not observed here. The cyclic lithium hydride trimer and tetramer clusters were also observed. Although the spontaneous reaction of 2 Li and H(2) to form (LiH)(2) occurs on annealing in solid H(2), the formation of higher clusters requires visible irradiation. We observed the simplest possible chemical reduction of dihydrogen using two lithium valence electrons to form the rhombic (LiH)(2) dimer.

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Stability and structure of LinH molecules (n=3–6): Experimental and density functional study

Cited by 15 publications

References 23 publications

Mechanisms of Hydrogen Generation from Tetrameric Clusters of Lithium Amidoborane

Mechanisms of Hydrogen Generation from Tetrameric Clusters of Lithium Amidoborane

Formation and ionization energies of small chlorine‐doped lithium clusters by thermal ionization mass spectrometry

Infrared Spectra and Theoretical Calculations of Lithium Hydride Clusters in Solid Hydrogen, Neon, and Argon

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