We report the results obtained via ab initio studies for electronic transmutation of beryllium to boron. According to the electronic transmutation concept, an element Z, by acquiring an extra electron, begins to exhibit similar chemical bonding and geometric structure properties of compounds composed of neigh- boring elements Z+1. Comprehensive searches for the most stable structures of LinBen and B-n (n = 3-5) demonstrate that the global minimum isomer of Li3Be3 resembles the chemical bonding and geometric structure of B-3. However, for n = 4 and 5, low lying isomers of the Be-n(n--) kernels-and not the global minimum-are what resemble their Bn counterparts.

The concept of electronic transmutation (ET) depicts the processes that by acquiring an extra electron, an element with the atomic number Z begins to have properties that were known to only belong to its neighboring element with the atomic number Z+1. Based on ET, signature compounds and chemical bonds that are composed of certain elements can now be designed and formed by other electronically transmutated elements. This Minireview summarizes the recent developments and applications of ET on both the theoretical and experimental fronts. Examples on the ET of Group 13 elements into Group 14 elements, Group 14 elements into Group 15 elements, and Group 15 elements into Group 16 elements are discussed. Compounds and chemical bonding composed of carbon, silicon, germanium, phosphorous, oxygen and sulfur now have analogues using transmutated boron, aluminum, gallium, silicon, nitrogen, and phosphorous.

Fluid circulation in the Earth's crust plays an essential role in surface, near surface, and deep crustal processes. Flow pathways are driven by hydraulic gradients but controlled by material permeability, which varies over many orders of magnitude and changes over time. Although millions of measurements of crustal properties have been made, including geophysical imaging and borehole tests, this vast amount of data and information has not been integrated into a comprehensive knowledge system. A community data infrastructure is needed to improve data access, enable large-scale synthetic analyses, and support representations of the subsurface in Earth system models. Here, we describe the motivation, vision, challenges, and an action plan for a community-governed, four-dimensional data system of the Earth's crustal structure, composition, and material properties from the surface down to the brittle-ductile transition. Such a system must not only be sufficiently flexible to support inquiries in many different domains of Earth science, but it must also be focused on characterizing the physical crustal properties of permeability and porosity, which have not yet been synthesized at a large scale. The DigitalCrust is envisioned as an interactive virtual exploration laboratory where models can be calibrated with empirical data and alternative hypotheses can be tested at a range of spatial scales. It must also support a community process for compiling and harmonizing models into regional syntheses of crustal properties. Sustained peer review from multiple disciplines will allow constant refinement in the ability of the system to inform science questions and societal challenges and to function as a dynamic library of our knowledge of Earth's crust.

A theoretical study of ozone isoelectronic Li3N3 species has been performed. Ab initio electronic structure calculations prove the viability of the ozone-like Li3N3 molecule that might become synthesized. The predicted Li3N3 species with a novel N3(3-) molecular motif possess structural and chemical bonding features similar to that of O3 molecules and can thus be considered as an "all-nitrogen ozone".

AbstractDFT‐based (CCSD(T), B3LYP) ab initio electronic structure calculations predict a novel viable polynitrogen molecule Li3N3 containing a N33‐ molecular motif, that possesses structural and chemical bonding features similar to that of O3 and can thus be considered as an “all‐nitrogen ozone”.

Potential energy surfaces of anionic B6Hy clusters were sampled using the coalescence kick method. We found that the planar to three-dimensional transition occurs in this system when y = 4. This is an important discovery because this transition suggests a major structural change as a function of dehydrogenation for the stoichiometric BnHn- polyhedral boranes. We also found that the B6H3- global minimum structure has an optical isomer. The chemical bonding patterns revealed by the adaptive natural density partitioning (AdNDP) analysis explain the geometric structure of all clusters presented here. From our chemical bonding analysis, we concluded that the 2D-3D transition occurs at B6H4- because the addition of one extra hydrogen atom further destroys the network of the peripheral 2c-2e B-B sigma-bonding, making planar structures less stable, and because the distorted octahedral structure provides some occupation of all sand p-AOs of boron, avoiding the presence of any empty atomic orbitals. Theoretical vertical electron detachment energies (VDEs) were calculated for comparison with future experimental work.

We performed global minimum searches for the B(n) H(n+2) (n=2-5) series and found that classical structures composed of 2c-2e B-H and B-B bonds become progressively less stable along the series. Relative energies increase from 2.9 kcal mol(-1) in B(2) H(4) to 62.3 kcal mol(-1) in B(5) H(7). We believe this occurs because boron atoms in the studied molecules are trying to avoid sp(2)  hybridization and trigonal structure at the boron atoms, as in that case one 2p-AO is empty, which is highly unfavorable. This affinity of boron to have some electron density on all 2p-AOs and avoiding having one 2p-AO empty is a main reason why classical structures are not the most stable configurations and why multicenter bonding is so important for the studied boron-hydride clusters as well as for pure boron clusters and boron compounds in general.

We propose a concept of electronic transmutation. According to this concept, elements, by acquiring an extra electron, begin to have the chemical bonding and geometric structure properties of compounds composed of neighboring elements. We demonstrate that boron, by acquiring an extra electron in boron–hydrogen compounds, forms molecular analogs of those of saturated hydrocarbons. We show by the means of quantum chemistry that the Li2B2H6 molecule in the most stable geometric form has the B2H62− kernel, which is isostructural to the C2H6 ethane molecule. We believe that this concept may have a significant effect on predicting new chemical compounds.

It was recently shown that the B3H8- anion can be produced during the reversible dehydrogenation of Mg(BH4)2 to Mg(B3H8)2 in the solid under moderate conditions. In this letter we performed a global minimum search for the B3H8- anion and identified the global minimum structure and one low-lying saddle point structure, which explains the flexural behavior of this anion. Chemical bonding analysis performed by Adaptive Natural Density Partitioning method revealed that the B3H8- anion is a σ-aromatic species. Calculated VDEs for the global minimum structure can help to interpret future anionic photoelectron spectroscopic study of this anion.

Potential energy surfaces of neutral and anionic B4H4 clusters were sampled using a Coalescence Kick method. A diverse set of global minimum structures and low-lying isomers was found for the studied clusters. Theoretical vertical electron detachment energies were calculated for the two lowest isomers of B4H4-, which could help to assign them in the future experimentally observed photoelectron spectra of the anion. Chemical bonding analysis for the global minimum structures and low-lying isomers of B4H4 and B4H4- was performed using the Adaptive Natural Density Partitioning method.

Potential energy surfaces of neutral and anionic B4H5 clusters were sampled using the Coalescence Kick method. We found that the neutral B4H5 cluster has two optical isomers as either a global minimum structure, or as almost degenerate isomers with the global minimum structure. For the B4H5- anion only the third lowest isomer forms a pair of optical isomers. The chemical bonding patterns revealed by the Adaptive Natural Density Partitioning (AdNDP) analysis can easily explain the geometric structure of even very exotic isomers and global minima. Theoretical vertical electron detachment energies (VDEs) were calculated for comparison with future experimental work.

We sampled potential energy surfaces of neutral and anionic B3Hy clusters using the Gradient Embedded Genetic Algorithm (GEGA) program at the B3LYP/3-21G level of theory. The lowest energy isomers were recalculated at the B3LYP/6-311++G**, MP2/6-311++G**, and CCSD(T)/6-311++G** levels of theory. We found a diverse set of global minimum structures and low-lying isomers for the studied clusters. The Adaptive Natural Density Partitioning (AdNDP) method was then used for chemical bonding analysis for all global minimum structures and low-lying isomers. The chemical bonding patterns revealed by the AdNDP analysis can easily explain the geometric structure of even very exotic isomers and global minima. 2-

We sampled potential energy surfaces of neutral and anionic B3Hy clusters using the Gradient Embedded Genetic Algorithm (GEGA) program at the B3LYP/3-21G level of theory. The lowest energy isomers were recalculated at the B3LYP/6-311 + +G**, MP2/6-311 ++G**, and CCSD(T)/6-311++G**levels of theory. We found a diverse set of global minimum structures and low-lying isomers for the studied clusters. The Adaptive Natural Density Partitioning (AdNDP) method was then used for chemical bonding analysis for all global minimum structures and low-lying isomers. The chemical bonding patterns revealed by the AdNDP analysis can easily explain the geometric structure of even very exotic isomers and global minima.