Communication: Highest occupied molecular orbital-lowest unoccupied molecular orbital gaps of doped silicon clusters from core level spectroscopy

A method to determine band gaps of size-selected and isolated nanoparticles by combination of valence band and core-level photoionization spectroscopy is presented. This approach is widely applicable and provides a convenient alternative to current standard techniques for the determination of band gaps by optical or photoelectron spectroscopy. A first application to vanadium doped silicon clusters confirms a striking size-dependence of their highest occupied-lowest unoccupied molecular orbital gaps.     

High-level ab initio predictions for the ionization energies and heats of formation of five-membered-ring molecules: thiophene, furan, pyrrole, 1,3-cyclopentadiene, and borole, C4H4X/C4H4X+ (X = S, O, NH, CH2, and BH)

The ionization energies (IEs) and heats of formation (ΔH°(f0)/ΔH°(f298)) for thiophene (C(4)H(4)S), furan (C(4)H(4)O), pyrrole (C(4)H(4)NH), 1,3-cyclopentadiene (C(4)H(4)CH(2)), and borole (C(4)H(4)BH) have been calculated by the wave function-based ab initio CCSD(T)/CBS approach, which involves the approximation to the complete basis set (CBS) limit at the coupled-cluster level with single and double excitations plus a quasi-perturbative triple excitation [CCSD(T)]. Where appropriate, the zero-point vibrational energy correction (ZPVE), the core-valence electronic correction (CV), and the scalar relativistic effect (SR) are included in these calculations. The respective CCSD(T)/CBS predictions for C(4)H(4)S, C(4)H(4)O, C(4)H(4)NH, and C(4)H(4)CH(2), being 8.888, 8.897, 8.222, and 8.582 eV, are in excellent agreement with the experimental values obtained from previous photoelectron and photoion measurements. The ΔH°(f0)/ΔH°(f298) values for the aforementioned molecules and their corresponding cations have also been predicted by the CCSD(T)/CBS method, and the results are compared with the available experimental data. The comparisons between the CCSD(T)/CBS predictions and the experimental values for C(4)H(4)S, C(4)H(4)O, C(4)H(4)NH, and C(4)H(4)CH(2) suggest that the CCSD(T)/CBS procedure is capable of predicting reliable IE values for five-membered-ring molecules with an uncertainty of ±13 meV. In view of the excellent agreements between the CCSD(T)/CBS predictions and the experimental values for C(4)H(4)S, C(4)H(4)O, C(4)H(4)NH, and C(4)H(4)CH(2), the similar CCSD(T)/CBS IE and ΔH°(f0)/ΔH°(f298) predictions for C(4)H(4)BH, whose thermochemical data are not readily available due to its reactive nature, should constitute a reliable data set. The CCSD(T)/CBS IE(C(4)H(4)BH) value is 8.868 eV, and ΔH°(f0)/ΔH°(f298) values for C(4)H(4)BH and C(4)H(4)BH(+) are 269.5/258.6 and 1125.1/1114.6 kJ/mol, respectively. The highest occupied molecular orbitals (HOMO) of C(4)H(4)S, C(4)H(4)O, C(4)H(4)NH, C(4)H(4)CH(2), and C(4)H(4)BH have also been studied by the natural bond orbital (NBO) method, and the extent of π-electron delocalization in these five-membered rings are discussed in correlation with their molecular structures and orbitals.     

A versatile palladium catalyst system for Suzuki-Miyaura coupling of alkenyl tosylates and mesylates

A general and effective palladium system for Suzuki-Miyaura coupling of alkenyl electrophiles under mild reaction conditions is reported. With the Pd(OAc)(2)/CM-phos system, a variety of alkenyl tosylates are coupled well with ArB(OH)(2). Moreover, the first successful examples of using alkenyl mesylates in alkenylation are also described.     

Epoxidation of alkenes and oxidation of alcohols with hydrogen peroxide catalyzed by a manganese(V) nitrido complex

The manganese(V) nitrido complex (PPh(4))(2)[Mn(N)(CN)(4)] is an active catalyst for alkene epoxidation and alcohol oxidation using H(2)O(2) as an oxidant. The catalytic oxidation is greatly enhanced by the addition of just one equivalent of acetic acid. The oxidation of ethene by this system has been studied computationally by the DFT method.     

Engineering of a redox protein for DNA-directed assembly

Engineered enzyme conjugate of the small laccase enzyme from Streptomyces coelicolor and zinc finger DNA binding domain from Zif268 is demonstrated to bind double stranded DNA in a site specific manner while retaining enzymatic activity.     

The radiation of polarized matter in a wave-guide of general cross-section with many dielectrics I

In this first part a straight general wave-guide with a perfectly conducting outer wall and several dielectrics, excited by an electrically generally polarized matter is considered and the electromagnetic field is determined.     

A model for phosphorus segregation at the silicon-silicon dioxide interface

A new model for phosphorus segregation at the Si-SiO₂ interface is derived and verified by experimental data. The model considers for the first time, a third phase, the interface layer itself, in addition to the Si and SiO₂ phases, and the dynamics of the three-phase system is described in terms of rate equations. In particular, the phosphorus compound formation in the interface layer (phosphorus pile-up), which renders the dopant electrically inactive to a large extent, is described as a competition of the dopant in silicon and in silicon dioxide in filling and depleting a constant density of interface traps. Our model allows an unambiguous correlation of the dopant concentration on both sides of the interface with the integral dose of the interface phosphorus pile-up. Experimental data for different phosphorus concentrations, different temperatures, and different oxidation ambients, including inert anneals, are fitted by a single curve.     

Jordan Structures in Harmonic Functions and Fourier Algebras on Homogeneous Spaces

We study the Jordan structures and geometry of bounded matrix-valued harmonic functions on a homogeneous space and their analogue, the harmonic functionals, in the setting of Fourier algebras of homogeneous spaces.Supported by EPSRC grant GR/G91182 and NSERC grant 7679.