Tug-of-war between classical and multicenter bonds in H-(Be)n-H species

Lundell, Katie A.; Boldyrev, Alexander I.

doi:10.1016/j.cplett.2018.03.044

Cited by 7 publications

(8 citation statements)

References 22 publications

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“… 27 In a recent literature, a tug-of-war between classical and multicenter bonding is demonstrated in Be containing H–(Be) n –H species. 28 By sharing electrons between Be and H atoms, multicenter bonding would exist and then reduce the total energy significantly. In this way, low dimensionality and unique structural topology may lead to exceptional properties of materials, e.g.…”

Section: Introductionmentioning

confidence: 99%

“…To the best of our knowledge, this is the rst report of 4c-2e bonds in the 2D beryllium hydride systems, quick aer its rst nding in beryllium hydride cluster of Be 4 H 2 in 2008. 28 It will explain the high stability for the longest Be-H bond (1.59Å). In summary, the above results reveal that the forming of the "banana" bonds in a-BeH 2 and 4c-2e bonds in the b-BeH 2 are responsible for their high structural stabilities.…”

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confidence: 99%

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Global minimum beryllium hydride sheet with novel negative Poisson's ratio: first-principles calculations

Aeberhard

et al. 2018

RSC Adv.

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As one of the most prominent metal-hydrides, beryllium hydride has received much attention over the past several decades, since 1978, and is considered as an important hydrogen storage material. By reducing the dimensionality from 3 to 2, the beryllium hydride monolayer is isoelectronic with graphene; thus the existence of its two-dimensional (2D) form is theoretically feasible and experimentally expected. However, little is known about its 2D form. In this work, by a global minimum search with the particle swarm optimization method via density functional theory computations, we predicted two new stable structures for the beryllium hydride sheets, named a-BeH 2 and b-BeH 2 monolayers. Both structures have more favorable thermodynamic stability than the recently reported planar square form (Nanoscale, 2017, 9, 8740), due to the forming of multicenter delocalized Be-H bonds. Utilizing the recently developed SSAdNDP method, we revealed that three-center-two-electron (3c-2e) delocalized Be-H bonds are formed in the a-BeH 2 monolayer, while for the b-BeH 2 monolayer, novel four-center-twoelectron (4c-2e) delocalized bonds are observed in the 2D system for the first time. These unique multicenter chemical bonds endow both a-and b-BeH 2 with high structural stabilities, which are further confirmed by the absence of imaginary modes in their phonon spectra, the favorable formation energies comparable to bulk and cluster beryllium hydride, and the high mechanical strength. These results indicate the potential for experimental synthesis. Furthermore, both a-and b-BeH 2 are widebandgap semiconductors, in which the a-BeH 2 has unusual mechanical properties with a negative Poisson's ratio of À0.19. If synthesized, it would attract interest both in experiment and theory, and be a new member of the 2D family isoelectronic with graphene.

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Section: Introductionmentioning

confidence: 99%

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confidence: 99%

Global minimum beryllium hydride sheet with novel negative Poisson's ratio: first-principles calculations

Aeberhard

et al. 2018

RSC Adv.

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“…These high population values for the NNA and ELF basin suggest that there is large electron localization between the Mg–Mg bonds. In the H‐(Be) n ‐H molecules, when n = 4, multicenter (in this case, 4‐center) bond among the four beryllium atoms is present in the system . We have computed the Multi‐center bond order (MCBO) among the four Mg atoms in our complex and it appears to be zero.…”

Section: Resultsmentioning

confidence: 99%

A Complex Containing Four Magnesium Atoms and Two Mg–Mg Bonds Behaving as an Electride

2019

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Herein, we report for the first time the stabilization of two Mg(I)–Mg(I) bonds simultaneously in the same complex. The β‐diketeminate based ligand is modified computationally and a new class of ligand, DippHL (Dipp = 2,6‐diisopropylphenyl) is designed that can hold two Mg atoms. Two such ligands stabilize two Mg22+ ions in a planar configuration and [Mg4(DippHL)2]2– complex is formed. Formation of a synthetically viable neutral [Mg4(DippHL)2]2–·2[K@CE]+ (CE = 18‐crown‐6 ether) complex is possible with the reduction of a proper precursor‐like [Mg2(DippHL)I2]– with potassium metals in toluene solvent and the reaction is exothermic in nature. The computed Mg–Mg bond lengths are in close agreement with that of the Mg–Mg single bond. The results obtained from natural bond orbital (NBO) and atoms in molecule (AIM) analyses confirm the presence of two Mg–Mg bonds in the complex. The complex under study has fulfilled all of the desired criteria and proved itself to be termed as an electride.

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“…16 [19][20][21][22] also focusing on the EPR properties 23 and most recently on the competition between multicenter and classical bonding. 24 However, no computations of the Renner-Tellersplit cation have yet been reported. Scheme 1.…”

Section: Toc Graphicsmentioning

confidence: 99%

Diborene: Generation and Photoelectron Spectroscopy of an Inorganic Biradical

Schleier

Humeniuk

Reusch

et al. 2018

J. Phys. Chem. Lett.

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Diborenes, R-BB-R′, are of current interest in inorganic chemistry because they offer the opportunity to tune the properties of a biradical by modifying the substituents of the diborene parent, HBBH. Here we synthesize the elusive diborene by H atom abstraction from diborane, B2H6, using fluorine atoms and report a vibrationally resolved photoelectron spectrum of the HBBH biradical. The spectrum is interpreted by comparison with high-level ab initio computations, taking into account the Renner–Teller splitting in the X+ 2Π ionic ground state, which show an excellent agreement with the experimental spectrum. An adiabatic ionization energy of 9.080 ± 0.015 eV was determined, and a vibrational progression in the boron–boron stretching vibration of 0.14 eV is visible. This is due to the reduction of bond order upon ionization, accompanied by an increase of the computed boron–boron bond length, R BB, from 1.514 to 1.606 Å.

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Tug-of-war between classical and multicenter bonds in H-(Be)n-H species

Cited by 7 publications

References 22 publications

Global minimum beryllium hydride sheet with novel negative Poisson's ratio: first-principles calculations

Global minimum beryllium hydride sheet with novel negative Poisson's ratio: first-principles calculations

A Complex Containing Four Magnesium Atoms and Two Mg–Mg Bonds Behaving as an Electride

Diborene: Generation and Photoelectron Spectroscopy of an Inorganic Biradical

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