We present a symmetry-based systematic approach to explore the structural and compositional richness of two-dimensional materials. We use a ‘combinatorial engine’ that constructs candidate compounds by occupying all possible Wyckoff positions for a certain space group with combinations of chemical elements. These combinations are restricted by imposing charge neutrality and the Pauling test for electronegativities. The structures are then pre-optimized with a specially crafted universal neural-network force-field, before a final step of geometry optimization using density-functional theory is performed. In this way we unveil an unprecedented variety of two-dimensional materials, covering the whole periodic table in more than 30 different stoichiometries of form A
- NSF-PAR ID:
- 10409600
- Publisher / Repository:
- IOP Publishing
- Date Published:
- Journal Name:
- 2D Materials
- Volume:
- 10
- Issue:
- 3
- ISSN:
- 2053-1583
- Page Range / eLocation ID:
- Article No. 035007
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
Because of their interesting structures and bonding and potentials as motifs for new nanomaterials, size-selected boron clusters have received tremendous interest in recent years. In particular, boron cluster anions (B n − ) have allowed systematic joint photoelectron spectroscopy and theoretical studies, revealing predominantly two-dimensional structures. The discovery of the planar B 36 cluster with a central hexagonal vacancy provided the first experimental evidence of the viability of 2D borons, giving rise to the concept of borophene. The finding of the B 40 cage cluster unveiled the existence of fullerene-like boron clusters (borospherenes). Metal-doping can significantly extend the structural and bonding repertoire of boron clusters. Main-group metals interact with boron through s/p orbitals, resulting in either half-sandwich-type structures or substitutional structures. Transition metals are more versatile in bonding with boron, forming a variety of structures including half-sandwich structures, metal-centered boron rings, and metal-centered boron drums. Transition metal atoms have also been found to be able to be doped into the plane of 2D boron clusters, suggesting the possibility of metalloborophenes. Early studies of di-metal-doped boron clusters focused on gold, revealing ladder-like boron structures with terminal gold atoms. Recent observations of highly symmetric Ta 2 B 6 − and Ln 2 B n − ( n = 7–9) clusters have established a family of inverse sandwich structures with monocyclic boron rings stabilized by two metal atoms. The study of size-selected boron and doped-boron clusters is a burgeoning field of research. Further investigations will continue to reveal more interesting structures and novel chemical bonding, paving the foundation for new boron-based chemical compounds and nanomaterials.more » « less
-
Abstract Exploring two dimensional (2D) materials is important for further developing the field of quantum materials. However, progress in 2D material development is limited by difficulties with their production. Specifically, freestanding 2D materials with bulk non-layered structures remain particularly challenging to prepare. Traditionally, chemical or mechanical exfoliation is employed for obtaining freestanding 2D materials, but these methods typically require layered starting materials. Here we put forth a method for obtaining thin layers of
β -Bi2O3, which has a three-dimensional covalent structure, by using chemical exfoliation. In this research, Na3Ni2BiO6was exfoliated with acid and water to obtainβ -Bi2O3nanosheets less than 10 nm in height and over 1µ m in lateral size. Our results open the possibility for further exploringβ -Bi2O3nanosheets to determine whether their properties change from the bulk to the nanoscale. Furthermore, this research may facilitate further progress in obtaining nanosheets of non-layered bulk materials using chemical exfoliation. -
Abstract Potential energy surface (PES) analyses at the SMD[MP2/6–311++G(d,p)] level and higher‐level energies up to MP4(fc,SDTQ) are reported for the fluorinated tertiary carbamate
N ‐ethyl‐N ‐(2,2,2‐trifluoroethyl) methyl carbamate (VII ) and its parent systemN ,N ‐dimethyl methyl carbamate (VI ). Emphasis is placed on the analysis of the rotational barrier about the CN carbamate bond and its interplay with the hybridization of theN ‐lone pair (NLP). All rotational transition state (TS) structures were found by computation of 1D relaxed rotational profiles but only 2D PES scans revealed the rotation‐inversion paths in a compelling fashion. We found four unique chiral minima ofVII , one pair each ofE‐ andZ ‐rotamers, and we determined theeight unique rotational TS structures associated with every possibleE /Z ‐isomerization path. It is a significant finding that all TS structures featureN ‐pyramidalization whereas the minima essentially contain sp2‐hybridized nitrogen. We will show that the TS stabilities are affected by the synergetic interplay between NLP/CO2repulsion minimization, NLP→σ*(CO) negative hyperconjugation, and two modes of intramolecular through‐space electrostatic stabilization. We demonstrate how Boltzmann statistics must be applied to determine the predicted experimental rotational barrier based on the energetics of all eight rotamerization pathways. The computed barrier forVII is in complete agreement with the experimentally measured barrier of the very similar fluorinated carbamateN ‐Boc‐N ‐(2,2,2‐trifluoroethyl)‐4‐aminobutan‐1‐olII . NMR properties ofVII were calculated with a variety of density functional/basis set combinations and Boltzmann averaging over theE‐ andZ ‐rotamers at our best theoretical level results in good agreement with experimental chemical shifts δ(13C) andJ (13C,19F) coupling constants ofII (within 6 %). -
Abstract Multiple bonds between boron and transition metals are known in many borylene (:BR) complexes via metal dπ→BR back‐donation, despite the electron deficiency of boron. An electron‐precise metal–boron triple bond was first observed in BiB2O−[Bi≡B−B≡O]−in which both boron atoms can be viewed as sp‐hybridized and the [B−BO]−fragment is isoelectronic to a carbyne (CR). To search for the first electron‐precise transition‐metal‐boron triple‐bond species, we have produced IrB2O−and ReB2O−and investigated them by photoelectron spectroscopy and quantum‐chemical calculations. The results allow to elucidate the structures and bonding in the two clusters. We find IrB2O−has a closed‐shell bent structure (
Cs ,1A ′) with BO−coordinated to an Ir≡B unit, (−OB)Ir≡B, whereas ReB2O−is linear (C ∞v ,3Σ−) with an electron‐precise Re≡B triple bond, [Re≡B−B≡O]−. The results suggest the intriguing possibility of synthesizing compounds with electron‐precise M≡B triple bonds analogous to classical carbyne systems. -
Abstract Multiple bonds between boron and transition metals are known in many borylene (:BR) complexes via metal dπ→BR back‐donation, despite the electron deficiency of boron. An electron‐precise metal–boron triple bond was first observed in BiB2O−[Bi≡B−B≡O]−in which both boron atoms can be viewed as sp‐hybridized and the [B−BO]−fragment is isoelectronic to a carbyne (CR). To search for the first electron‐precise transition‐metal‐boron triple‐bond species, we have produced IrB2O−and ReB2O−and investigated them by photoelectron spectroscopy and quantum‐chemical calculations. The results allow to elucidate the structures and bonding in the two clusters. We find IrB2O−has a closed‐shell bent structure (
Cs ,1A ′) with BO−coordinated to an Ir≡B unit, (−OB)Ir≡B, whereas ReB2O−is linear (C ∞v ,3Σ−) with an electron‐precise Re≡B triple bond, [Re≡B−B≡O]−. The results suggest the intriguing possibility of synthesizing compounds with electron‐precise M≡B triple bonds analogous to classical carbyne systems.