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Abstract
In the present work, a modern method of crystal structure prediction, namely USPEX conjugated with density functional theory (DFT) calculations, was used to predict the new stable structures of BnPn (n = 12, 24) clusters. Since B12N12 and B24N24 fullerenes have been synthesized experimentally, it motivated us to explore the structural prediction of B12P12 and B24P24 clusters. All new structures were predicted to be energetically favorable with negative binding energy in the range from −4.7 to −4.8 eV per atom, suggesting good experimental feasibility for the synthesis of these structures. Our search for the most stable structure of BnPn clusters led us to classify the predicted structures into two completely distinct structures such as α-BnPn and β-BnPn phases. In α-BnPn, each phosphorus atom is doped into a boron atom, whereas B atoms form a Bn unit. On the other hand, each boron atom in the β-phase was bonded to a phosphorus atom to make a fullerene-like cage structure. Besides, theoretical simulations determined that α-BnPn structures, especially α-B24P24, show superior oxidation resistance and also, both α-BnPn and β-BnPn exhibit better thermal stability; the upper limit temperature that structures can tolerance is 900 K. The electronic properties of new compounds illustrate a higher degree of absorption in the UV and visible-region with the absorption coefficient larger than 105 cm−1, which suggests a wide range of opportunities for advanced optoelectronic applications. The β-BnPn phase has suitable band alignments in the visible-light excitation region, which will produce enhanced photocatalytic activities. On the other hand, α-BnPn structures with modest band gap exhibit large second hyperpolarizability, which are anticipated to have excellent potential as second-order non-linear optical (NLO) materials.
Highlights
In the past decade, many attempts have been made to discover non-carbon fullerene-like structures based on their unique properties.[1,2,3,4,5,6,7,8,9] The structural and electronic properties of clusters form an intermediate state between the individual atoms and crystals
In the a-phases, each phosphorus atom is doped into a boron atom while the B atoms form a Bn unit
We explored the new stable structure of BnPn (n 1⁄4 12, 24) clusters with a modern method of crystal structure prediction, USPEX conjugated with spin-polarized rstprinciples calculations
Summary
Many attempts have been made to discover non-carbon fullerene-like structures based on their unique properties.[1,2,3,4,5,6,7,8,9] The structural and electronic properties of clusters form an intermediate state between the individual atoms and crystals. In all the previous studies, X12Y12 and X24Y24 clusters have been considered as fullerene-like structures, which consist of four-, six-, and eight-membered rings, and have large HOMO–LUMO gaps, almost zero dipole moment, and nearly zero hyperpolarizability.[31] It should be mentioned that in all the previous studies, (XY)n clusters (X 1⁄4 B, Al, Ga, and Y 1⁄4 P, As) were made directly by replacing B and N atoms of the already known structures of the (BN)n cages with other atoms, the bonding length and angle are adjusted by further calculations Based on this strategy, the main questions are that whether this method is correct and whether this method give the lowest energy structure. It should be noted that the B12N12 and B24N24 fullerenes have been synthesized experimentally; the B12P12 and B24P24 structures were chosen
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