Selected boron, aluminum, and gallium trihalide and trihydride anions

Brzeski, Jakub; Czapla, Marcin; Skurski, Piotr; Simons, Jack

doi:10.1016/j.chemphys.2016.05.008

Cited by 4 publications

(10 citation statements)

References 39 publications

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“…In searching for the lowest energy structures, we did consider geometries such as H–Mg–AlH 2 but in all cases such structures were found to be considerably higher in energy than those discussed here. In ref we studied the BH 3 , AlH 3 , and GaH 3 fragments and their anions and in ref we studied Be and Mg bonded to BH 3 and the anions of these two complexes, and we will include some discussion of these species in the present work to offer comparisons. For some of the species, we also found higher energy local minima having θ values of opposite sign to those of our reported global minima.…”

Section: Resultsmentioning

confidence: 99%

“…In the course of our ab initio studies (based on a CCSD(T)/aug-cc-pV5Z theoretical approach), we established the adiabatic electron affinity (EA) of BH 3 and the vertical electron detachment energy (VDE) of (BH 3 ) − to be 0.02 and 0.04 eV, respectively, and confirmed the planar D 3 h -symmetry structure of both neutral BH 3 and its daughter BH 3 – anion. Unlike BH 3 – , AlH 3 – and GaH 3 – were found to adopt nonplanar geometries and to bind an excess electron more strongly (the EAs of AlH 3 and GaH 3 were calculated to be 0.31 and 0.26 eV, respectively, while the VDEs of AlH 3 – and GaH 3 – were evaluated to be 0.41 and 0.37 eV, respectively) …”

Section: Introductionmentioning

confidence: 99%

“…Due to the fact that earlier literature reports describing the possibility of an excess electron binding by borane, alane, and gallane were contradictory (for BH 3 ), 16−20 scarce and outdated (for AlH 3 ) 21,22 or absent (for GaH 3 ), we recently investigated the issue of the stability of BH 3 − , AlH 3 − , and GaH 3 − anions. 23 In the course of our ab initio studies (based on a CCSD(T)/ aug-cc-pV5Z theoretical approach), we established the adiabatic electron affinity (EA) of BH 3 and the vertical electron detachment energy (VDE) of (BH 3 ) − to be 0.02 and 0.04 eV, respectively, and confirmed the planar D 3h -symmetry structure of both neutral BH 3 and its daughter BH Unlike BH 3 − , AlH 3 − and GaH 3 − were found to adopt nonplanar geometries and to bind an excess electron more strongly (the EAs of AlH 3 and GaH 3 were calculated to be 0.31 and 0.26 eV, respectively, while the VDEs of AlH 3 − and GaH 3 − were evaluated to be 0.41 and 0.37 eV, respectively). 23 In our most recent paper, 24 we investigated compounds formed by an attachment of an alkaline earth metal atom (Be or Mg) to BH 3 .…”

Section: Introductionmentioning

confidence: 99%

“…Due to the fact that earlier literature reports describing the possibility of an excess electron binding by borane, alane, and gallane were contradictory (for BH 3 ), − scarce and outdated (for AlH 3 ) , or absent (for GaH 3 ), we recently investigated the issue of the stability of BH 3 – , AlH 3 – , and GaH 3 – anions . In the course of our ab initio studies (based on a CCSD(T)/aug-cc-pV5Z theoretical approach), we established the adiabatic electron affinity (EA) of BH 3 and the vertical electron detachment energy (VDE) of (BH 3 ) − to be 0.02 and 0.04 eV, respectively, and confirmed the planar D 3 h -symmetry structure of both neutral BH 3 and its daughter BH 3 – anion.…”

Section: Introductionmentioning

confidence: 99%

“…In our most recent paper, we investigated compounds formed by an attachment of an alkaline earth metal atom (Be or Mg) to BH 3 . We studied such a functionalization of the simplest borane mostly because we had become intrigued by the possibility of forming electronically stable anions by assembling two closed-shell species whose tendency to bind an excess negative charge is either zero (neither Be nor Mg forms a stable anion) or tiny (BH 3 ) . Our calculations revealed that the molecules assembled from these species are capable of forming electronically and thermodynamically stable BeBH 3 – and MgBH 3 – anions whose equilibrium structures are similar to those of their corresponding BeBH 3 and MgBH 3 neutral parents.…”

Section: Introductionmentioning

confidence: 99%

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Unusual and Conventional Dative Bond Formation by s² Lone Pair Donation from Alkaline Earth Metal Atoms to BH₃, AlH₃, and GaH₃

et al. 2020

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Using ab initio electronic structure methods with flexible atomic orbital basis sets, we examined the nature of the bonding arising from donation of an ns2 electron pair on an alkaline earth atom (Mg or Ca) into a vacant n′p orbital on the group 13 atom of BH3, AlH3, or GaH3. We also examined what happens when an excess electron is attached to form corresponding molecular anions. Although the geometries of MgBH3, MgAlH3, MgGaH3, and CaBH3 are found to be much as one would expect for datively bound molecules, CaAlH3 and CaGaH3 were found to have very unusual geometries in that their Al–H or Ga–H bonds are directed toward the Ca atom rather than away, as in the other compounds. Internal electrostatic Coulomb attractions between the partially positively charged Ca center and the partially negatively charged H centers were suggested as a source of these unusual geometries. The other novel finding is that the electron affinities (EAs) of all six M′–MH3 species lie in the 0.7–1.0 eV range, which is suggestive of ionic electronic structures for the neutrals even though the partial charges on the alkaline earth centers are as low as 0.3 atomic units. Partial positive charge on the alkaline earth atoms combined with substantial electron affinities of the BH3, AlH3, and GaH3 groups, but only when distorted from planar geometries, were suggested to be the primary contributors to the large EAs.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%