Analytic energy gradients of the optimized effective potential method

The analytic energy gradients of the optimized effective potential (OEP) method in density-functional theory are developed. Their implementation in the direct optimization approach of Yang and Wu [Phys. Rev. Lett. 89, 143002 (2002)] and Wu and Yang [J. Theor. Comput. Chem. 2, 627 (2003)] are carried out and the validity is confirmed by comparison with corresponding gradients calculated via numerical finite difference. These gradients are then used to perform geometry optimizations on a test set of molecules. It is found that exchange-only OEP (EXX) molecular geometries are very close to the Hartree-Fock results and that the difference between the B3LYP and OEP-B3LYP results is negligible. When the energy is expressed in terms of a functional of Kohn-Sham orbitals, or in terms of a Kohn-Sham potential, the OEP becomes the only way to perform density-functional calculations and the present development in the OEP method should play an important role in the applications of orbital or potential functionals.     

Chemical principles underpinning the performance of the metal–organic framework HKUST-1

A common feature of multi-functional metal–organic frameworks is a metal dimer in the form of a paddlewheel, as found in the structure of Cu₃(btc)₂ (HKUST-1). The HKUST-1 framework demonstrates exceptional gas storage, sensing and separation, catalytic activity and, in recent studies, unprecedented ionic and electrical conductivity. These results are a promising step towards the real-world application of metal–organic materials. In this perspective, we discuss progress in the understanding of the electronic, magnetic and physical properties of HKUST-1, representative of the larger family of Cu···Cu containing metal–organic frameworks. We highlight the chemical interactions that give rise to its favourable properties, and which make this material well suited to a range of technological applications. From this analysis, we postulate key design principles for tailoring novel high-performance hybrid frameworks.     

ChemInform Abstract: Band Edge Electronic Structure of BiVO4: Elucidating the Role of the Bi s and V d Orbitals.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

The analytic spread of codimension two monomial varieties

Let ${\rm} A=k[{u_{1}^{a_{1}}},{u_{2}^{a_{2}}},\dots,{u_{n}^{a_{n}}},{u_{1}^{c_{1}}} \dots {u_{n}^{c_{n}}},{u_{1}^{b_{1}}} \dots {u_{n}^{b_{n}}}]\ \subset k[{u_{1}}, \dots {u_{n}}],$ where, a_j, b_j, C_j ∈ ?, a_j > 0, (b_j, C_j) ≠ (0,0) for 1 ≤ j ≤ n, and, further ${\underline b}:=\ ({b_{1}}, \dots,{b_{n}})\ \not=\ 0 $ and ${\underline c}:=\ ({c_{1}}, \dots,{c_{n}})\ \not=\ 0 $ . The main result says that the defining ideal I ? m = (x₁,…, x_n, y, z) ? k[x₁,…, x_n, y, z] of the semigroup ring A has analytic spread ?(I_m) at most three.     

CARS probe of RDX decomposition

Coherent anti-Stokes Raman scattering (CARS) was used to probe RDX (hexahydro-1,3,5-trinitro-s-triazine) in a carbohydrate matrix burning unconfined in air. Several spectral regions were scanned in an attempt to document the transient species of the RDX combustion for use in determining decomposition mechanisms.     

Polymorph exploration of bismuth stannate using first-principles phonon mode mapping

Accurately modelling polymorphism in crystalline solids remains a key challenge in computational chemistry. In this work, we apply a theoretically-rigorous phonon mode-mapping approach to understand the polymorphism in the ternary metal oxide Bi₂Sn₂O₇. Starting from the high-temperature cubic pyrochlore aristotype, we systematically explore the structural potential-energy surface and recover the two known low-temperature phases alongside three new metastable phases, together with the transition pathways connecting them. This first-principles lattice-dynamics method is completely general and provides a practical means to identify and characterise the stable polymorphs and phase transitions in materials with complex crystal structures.

Using a phonon mode-mapping approach, we recover the known experimental phases of the ternary oxide Bi₂Sn₂O₇ and identify three new metastable phases, highlighting the utility of the method for polymorph prediction on many other complex materials.