Accurate Measurement of the Optical Constants n and k for a Series of 57 Inorganic and Organic Liquids for Optical Modeling and Detection.

For optical modeling and other purposes, we have created a library of 57 liquids for which we have measured the complex optical constants n and k. These liquids vary in their nature, ranging in properties that include chemical structure, optical band strength, volatility, and viscosity. By obtaining the optical constants, one can model most optical phenomena in media and at interfaces including reflection, refraction, and dispersion.

Activation of the S-H group in Fe(mu(2)-SH)Fe clusters: S-H bond strengths and free radical reactivity of the Fe(mu(2)-SH)Fe cluster.

Absolute rate constants were determined for the abstraction of hydrogen atoms from (OC)(3)Fe(mu-SH)(2)Fe(CO)(3) (Fe(2)S(2)H(2)) and (OC)(3)Fe(mu-SCH(3))(mu-SH)Fe(CO)(3) (Fe(2)S(2)MeH) by benzyl radicals in benzene. From the temperature-dependent rate data for Fe(2)S(2)H(2), DeltaH(++) and DeltaS(++) were determined to be 2.03 +/- 0.

Formation and reactivity of a persistent radical in a dinuclear molybdenum complex.

The reactivity of the S-H bond in Cp*Mo(mu-S) 2(mu-SMe)(mu-SH)MoCp* ( S 4 MeH) has been explored by determination of kinetics of hydrogen atom abstraction to form the radical Cp*Mo(mu-S) 3(mu-SMe)MoCp* ( S 4 Me*), as well as reaction of hydrogen with the radical-dimer equilibrium to reform the S-H complex. From the temperature dependent rate data for the abstraction of hydrogen atom by benzyl radical, Delta H (double dagger) and Delta S (double dagger) were determined to be 1.54 +/- 0.

Actinide sequestration using self-assembled monolayers on mesoporous supports.

Surfactant templated synthesis of mesoporous ceramics provides a versatile foundation upon which to create high efficiency environmental sorbents. These nanoporous ceramic oxides condense a huge amount of surface area into a very small volume. The ceramic oxide interface is receptive to surface functionalization through molecular self-assembly.

Effects of template and precursor chemistry on structure and properties of mesoporous TiO2 thin films.

Mesoporous TiO2 thin films were synthesized by sol-gel processing using an aqueous-based, inexpensive, and environmentally friendly precursor and cationic surfactants as templates under mild reaction conditions. The films were prepared by spin-coating on glass substrates followed by calcination to remove the surfactant. N2 sorption, X-ray diffraction, and transmission electron microscopy were used to characterize the porosity, pore size, and pore structure before and after calcination.

Activation of the sulfhydryl group by Mo centers: kinetics of reaction of benzyl radical with a binuclear Mo(micro-SH)Mo complex and with arene and alkane thiols.

This paper provides evidence from kinetic experiments and electronic structure calculations of a significantly reduced S-H bond strength in the Mo(micro-SH)Mo function in the homogeneous catalyst model, CpMo(micro-S)(2)(micro-SH)(2)MoCp (1, Cp = eta(5)-cyclopentadienyl). The reactivity of 1 was explored by determination of a rate expression for hydrogen atom abstraction by benzyl radical from 1 (log(k(abs)/M(-)(1) s(-)(1)) = (9.07 +/- 0.

Effect of humidity treatments on porosity and mechanical integrity of mesoporous silica films.

The beneficial effects humidity treatments have on molecularly templated mesoporous silica films with respect to elastic modulus, with minimal detrimental effects on porosity and dielectric constant, were identified.

Effects of trace metals and organic additives on porosity and dielectric constant of high purity mesoporous silica films.

The beneficial effects that alkali metal and alkylammonium salt additions to molecularly templated silica sols have on the resulting mesoporous silica films formed from evaporative-coating methods with respect to porosity, elastic modulus, dielectric constant, and film surface uniformity were investigated and identified.

Synthesis of carbamoylphosphonate silanes for the selective sequestration of actinides.

The synthesis of carbamoylphosphonate silanes (CMPO analogs) designed for sequestering actinide cations in self-assembled monolayers on mesoporous supports (SAMMS) is described.