Lattice strain effects on CO oxidation on Pt(111)

Surface strain plays a major role in determining the rate limiting step and catalytic activity of platinum for CO oxidation.     

Design of electroceramic materials using artificial neural networks and multiobjective evolutionary algorithms

We describe the computational design of electroceramic materials with optimal permittivity for application as electronic components. Given the difficulty of large-scale manufacture and characterization of these materials, including the theoretical prediction of their materials properties by conventional means, our approach is based on a recently established database containing composition and property information for a wide range of ceramic compounds. The electroceramic materials composition-function relationship is encapsulated by an artificial neural network which is used as one of the objectives in a multiobjective evolutionary algorithm. Evolutionary algorithms are stochastic optimization techniques which we employ to search for optimal materials based on chemical composition. The other objectives optimized include the reliability of the neural network prediction and the overall electrostatic charge of the material. The evolutionary algorithm searches for materials which simultaneously have high relative permittivity, minimum overall charge, and good prediction reliability. We find that we are able to predict a range of new electroceramic materials with varying degrees of reliability. In some cases the materials are similar to those contained in the database; in others, completely new materials are predicted.     

Zn(H2O)4][Zn2Sn3Se9(MeNH2)]: a robust open framework chalcogenide with a large nonlinear optical response

[Zn(H2O)4][Zn2Sn3Se9(MeNH2)] has an open polar framework based on supertetrahedral clusters with a unique double connectivity mode and exhibits a strong second harmonic generation response, excellent acid stability and proton exchange capacity.     

Exact statistical mechanical lattice model and classical Lindemann theory of melting of inert gas solids

A modified form of Lindemann’s model shows that the melting points of the heavy inert gases and other effectively spherical molecular species are proportional to the depths of their diatomic potential wells. The success of the model when compared with experiment seems to rely on the almost constant value of the ratio of the fractional volume and entropy changes during fusion. The Lindemann proposal can be incorporated into an exactly treated statistical mechanical lattice model utilising expandable clusters which reproduces the solid–liquid melting phenomenon for argon with a realistic volume change and melting line.     

Polyoxomolybdenum(V/VI)-sulfite compounds: synthesis, structural, and physical studies

Reaction of Na(2)Mo(VI)O(4) x 2H(2)O with (NH(4))(2)SO(3) in the mixed-solvent system H(2)O/CH(3)CN (pH = 5) resulted in the formation of the tetranuclear cluster (NH(4))(4)[Mo(4)(VI)SO(16)] x H(2)O (1), while the same reaction in acidic aqueous solution (pH = 5) yielded (NH(4))(4)[Mo(5)(VI)S(2)O(21)] x 3H(2)O (2). Compound {(H(2)bipy)(2)[Mo(5)(VI)S(2)O(21)] x H(2)O}(x) (3) was obtained from the reaction of aqueous acidic solution of Na(2)Mo(VI)O(4) x 2H(2)O with (NH(4))(2)SO(3) (pH = 2.5) and 4,4'-bipyridine (4,4'-bipy). The mixed metal/sulfite species (NH(4))(7)[Co(III)(Mo(2)(V)O(4))(NH(3))(SO(3))(6)] x 4H(2)O (4) was synthesized by reacting Na(2)Mo(VI)O(4) x 2H(2)O with CoCl(2) x 6H(2)O and (NH(4))(2)SO(3) with precise control of pH (5.3) through a redox reaction. The X-ray crystal structures of compounds 1, 2, and 4 were determined. The structure of compound 1 consists of a ring of four alternately face- and edge-sharing Mo(VI)O(6) octahedra capped by the trigonal pyramidal sulfite anion, while at the base of the Mo(4) ring is an oxo group which is asymmetrically shared by all four molybdenum atoms. Compound 3 is based on the Strandberg-type heteropolyion [Mo(5)(VI)S(2)O(21)](4-), and these coordinatively saturated clusters are joined by diprotonated 4,4'-H(2)bipy(2+) through strong hydrogen bonds. Compound 3 crystallizes in the chiral space group C2. The structure of compound 4 consists of a novel trinuclear [Co(III)Mo(2)(V)SO(3)(2-)] cluster. The chiral compound 3 exhibits nonlinear optical (NLO) and photoluminescence properties. The assignment of the sulfite bands in the IR spectrum of 4 has been carried out by density functional calculations. The cobalt in 4 is a d(6) octahedral low-spin metal atom as it was evidenced by magnetic susceptibility measurements, cw EPR, BVS, and DFT calculations. The IR and solid-state UV-vis spectra as well as the thermogravimetric analyses of compounds 1-4 are also reported.     

Sequestration of Heavy Metals from Water with Layered Metal Sulfides

Extraordinarily effective heavy metal ion scavenger : We show here that the material K_2xMn_xSn_3?xS₆ (x=0.5–0.95) (KMS‐1) overcomes the limitations of the known heavy metal ion sorbents, showing the capability to rapidly reduce the concentrations of Cd, Hg, and Pb ions well‐below the legally acceptable levels for drinking water. KMS‐1 is inexpensive, easily prepared in large quantities, and may play a role in addressing the global problem of water contamination with heavy metal ions. The paradigm of heavy metal ion absorption of KMS‐1 is the ability to form very strong M? S bonds.

     

Deconvolution filters to enhance resolution of dense time-of-flight survey spectra in the time-lag optimization range

By applying time-domain filters to time-of-flight (TOF) mass spectrometry signals, we have simultaneously smoothed and narrowed spectra resulting in improved resolution and increased signal-to-noise ratios. This filtering procedure has an advantage over detailed curve fitting of spectra in the case of large dense spectra, when neither the location nor the number of mass peaks is known a priori. This time series method is directly applicable in the time lag optimization range, where point density per peak is constant. We present a systematic methodology to optimize the filters according to any desired figure of merit, illustrating the procedure by optimizing the signal-to-noise per unit bandwidth of matrix-assisted laser desorption/ionization (MALDI) data. We also introduce a nonlinear filter that reduces the spurious structure that often accompanies deconvolution filters. The net result of the application of these filters is that we can identify new structures in dense MALDI-TOF data, clearly showing small adducts to heavy biomolecules.     

Pentanuclear complexes with unusual structural topologies from the initial use of two aliphatic amino-alcohol ligands in Fe chemistry

Five novel pentanuclear Fe(3+) clusters with the aliphatic amino-alcohol ligands 3-amino-1-propanol (Hap) and 2-(hydroxymethyl)piperidine (Hhmpip) [Fe(5)(μ(3)-Ο)(2)(L)(4)(O(2)CR)(7)] [L = ap(-), R = Ph (1); L = ap(-), R = C(CH(3))(3) (2); L = hmpip(-), R = Ph (3); L = hmpip(-), R = C(CH(3))(3) (4)] and [Fe(5)(μ(4)-Ο)(μ(3)-Ο)(O(2)CC(CH(3))(3))(8)(ap)(2)Cl(HO(2)CC(CH(3))(3))] (5) are reported. Compounds 1-4 were prepared from reactions of preformed trinuclear Fe(3+) clusters with the ligands in a molar ratio 1 : 5 in MeCN (1, 3, 4) or DMF (2), whereas compound 5 was prepared from the reaction of FeCl(3) with Hap in the presence of HO(2)CC(CH(3))(3) in a molar ratio 1 : 3 : 2 in MeCN. To the best of our knowledge, 1-5 are the first examples of Fe(3+) complexes with the ligands Hap and Hhmpip. The structures of 1-4 are composed of a quasi-planar [Fe(5)(μ(3)-O)(2)](11+) core which consists of two vertex-sharing [Fe(3)(μ(3)-O)](7+) triangles. The structure of 5 is based on the [Fe(5)(μ(4)-O)(μ(3)-O)](11+) core, in which the five Fe(3+) ions adopt a monocapped trigonal pyramidal topology. Variable-temperature magnetic susceptibility measurements on powdered microcrystalline samples of 1 and 5 revealed the existence of antiferromagnetic interactions which led to an S = 5/2 ground state. M?ssbauer spectroscopy studies on powdered microcrystalline samples of 1 and 5 confirmed that all iron ions of both complexes are in the Fe(3+) (S = 5/2) state. The variation of the ligand environment in the various iron sites was reflected in their different quadruple splitting parameters. At T < 50 K the M?ssbauer spectra indicated the onset of spin relaxation effects in the time scale of the technique (10(-7)-10(-8) s).     

CO2 hydrogenation to formic acid on Ni(110)

Hydrogen (H) in the subsurface of transition-metal surfaces exhibits unique reactivity for heterogeneously catalyzed hydrogenation reactions. Here, we explore the potential of subsurface H for hydrogenating carbon dioxide (CO₂) on Ni(110). The energetics of surface and subsurface H reacting with surface CO₂ to form formate, carboxyl, and formic acid on Ni(110) is systematically studied using self-consistent, spin-polarized, periodic density functional theory (DFT-GGA-PW91) calculations. We show that on Ni(110), CO₂ can be hydrogenated to formate by surface H. However, further hydrogenation of formate to formic acid by surface H is hindered by a larger activation energy barrier. The relative energetics of hydrogenation barriers is reversed for the carboxyl-mediated route to formic acid. We suggest that the energetics of subsurface H emerging to the surface is suitable for providing the extra energy needed to overcome the barrier to formate hydrogenation. CO₂ hydrogenation to formic acid could take place on Ni(110) when subsurface H is available to react with CO₂. Additional electronic-structure based dynamic calculations would be needed to elucidate the detailed reaction paths for these transformations.