Predicting solid-state heats of formation of newly synthesized polynitrogen materials by using quantum mechanical calculations.

We present density functional theory level predictions and analysis of the basic properties of newly synthesized high-nitrogen compounds together with 3,6-bis(2H-tetrazol-5-yl)-1,2,4,5-tetrazine (BTT) and 3,3'-azobis(6-amino-1,2,4,5-tetrazine) (DAAT), for which experimental data are available. The newly synthesized high-nitrogen compounds are based on tricycle fused 1,2,4-triazine and 1,2,4,5-tetrazine heterocycles. In this work, the molecules BTT and DAAT have been studied in order to validate the theoretical approach and to facilitate further progress developments for the molecules of interest. Molecular structural properties are clarified, and IR spectra predictions are provided to help detection of those compounds in the experiment. The energy content of the molecules in the gas phase is evaluated by calculating standard enthalpies of formation, by using a special selection of isodesmic reaction paths. We also include estimates of the condensed-phase heats of formation and heats of sublimation in the framework of the Politzer approach. The obtained properties are consistent with those new high-nitrogen compounds being a promising set of advanced energetic materials.

The peculiar electronic structure of PbSe quantum dots.

PbSe is a pseudo-II-VI material distinguished from ordinary II-VI's (e.g., CdSe, ZnSe) by having both its valence band maximum (VBM) and its conduction band minimum (CBM) located at the fourfold-degenerate L-point in the Brillouin zone. It turns out that this feature dramatically affects the properties of the nanosystem. We have calculated the electronic and optical properties of PbSe quantum dots using an atomistic pseudopotential method, finding that the electronic structure is different from that of ordinary II-VI's and, at the same time, is more subtle than what k.p or tight-binding calculations have suggested previously for PbSe. We find the following in PbSe dots: (i) The intraband (valence-to-valence and conduction-to-conduction) as well as interband (valence-to-conduction) excitations involve the massively split L-manifold states. (ii) In contrast to previous suggestions that the spacings between valence band levels will equal those between conduction band levels (because the corresponding effective-masses me approximately mh are similar), we find a densely spaced hole manifold and much sparser electron manifold. This finding reflects the existence of a few valence band maxima in bulk PbSe within approximately 500 meV. This result reverses previous expectations of slow hole cooling in PbSe dots. (iii) The calculated optical absorption spectrum reproduces the measured absorption peak that had previously been attributed to the forbidden 1Sh --> 1Pe or 1Ph --> 1Se transitions on the basis of k.p calculations. However, we find that this transition corresponds to an allowed 1Ph --> 1Pe excitation arising mainly from bulk states near the L valleys on the Gamma-L lines of the Brillouin zone. We discuss this reinterpretation of numerous experimental results.

Systematic method to new phases of polymeric nitrogen under high pressure.

A systematic method to unravel a large class of single-bonded (SB) polymeric phases of nitrogen under high pressure is presented. The approach is based on the combinatorial generation of different Peierls-like distortions of a given reference structure that maintain the threefold connectivity of SB nitrogen, followed by first-principles calculations. Using an eight atom simple cubic reference structure, the approach not only recovers all four SB nitrogen phases reported to date, but eight new metastable structures (confirmed by phonon density of states calculations) are found. Basic properties of the structures are computed and the trends analyzed. Extensions to the method are straightforward and should lead to the discovery of more phases of polynitrogen.

Searching for alloy configurations with target physical properties: impurity design via a genetic algorithm inverse band structure approach.

The ability to artificially grow different configurations of semiconductor alloys--random structures, spontaneously ordered and layered superlattices--raises the issue of how different alloy configurations may lead to new and different alloy physical properties. We address this question in the context of nitrogen impurities in GaP, which form deep levels in the gap whose energy and optical absorption sensitively depend on configuration. We use the "inverse band structure" approach in which we first specify a desired target physical property (such as the deepest nitrogen level, or lowest strain configuration), and then we search, via genetic algorithm, for the alloy atomic configurations that have this property. We discover the essential structural motifs leading to such target properties. This strategy opens the way to efficient alloy design.

First-principles combinatorial design of transition temperatures in multicomponent systems: the case of Mn in GaAs.

The transition temperature TC of multicomponent systems--ferromagnetic, superconducting, or ferroelectric--depends strongly on the atomic arrangement, but an exhaustive search of all configurations for those that optimize TC is difficult, due to the astronomically large number of possibilities. Here we address this problem by parametrizing the TC of a set of approximately 50 input configurations, calculated from first principles, in terms of configuration variables ("cluster expansion"). Once established, this expansion allows us to search almost effortlessly the transition temperature of arbitrary configurations. We apply this approach to search for the configuration of Mn dopants in GaAs having the highest ferromagnetic Curie temperature. Our general approach of cluster expanding physical properties opens the way to design based on exploring a large space of configurations.