Rate constants for the gas-phase reactions of OH radicals and Cl atoms with n-alkyl nitrites at atmospheric pressure and 298 K

Rate constants for the reactions of OH radicals and Cl atoms with CH₃ONO, C₂H₅ONO, n-C₃H₇ONO, n-C₄H₉ONO, and n-C₅H₁₁ONO have been determined at 298 ± 2 K and a total pressure of approximately 1 atm. The OH rate data were obtained using both the absolute rate technique of pulse radiolysis combined with kinetic spectroscopy and a relative rate method involving simultaneous measurement of the loss of the nitrite and the reference compound. The Cl rate constants were measured using the relative rate method. Values of the rate constants in units of 10^?13 cm³ molecule^?1 s^?1 are:

Structural and energetic properties of RMX3-NH3 complexes

We have explored the structural and energetic properties of a series of RMX₃-NH₃ (M=Si, Ge; X=F, Cl; R=CH₃, C₆H₅) complexes using density functional theory and low-temperature infrared spectroscopy. In the minimum-energy structures, the NH₃ binds axially to the metal, opposite a halogen, while the organic group resides in an equatorial site. Remarkably, the primary mode of interaction in several of these systems seems to be hydrogen bonding (C-H--N) rather than a tetrel (N→M) interaction. This is particularly clear for the RMCl₃-NH₃ complexes, and analyses of the charge distributions of the acid fragment corroborate this assessment. We also identified a set of metastable geometries in which the ammonia binds opposite the organic substituent in an axial orientation. Acid fragment charge analyses also provide a clear rationale as to why these configurations are less stable than the minimum-energy structures. Matrix-isolation infrared spectra provide clear evidence for the occurrence of the minimum-energy form of CH₃SiCl₃–NH₃, but analogous results for CH₃GeCl₃–NH₃ are less conclusive. Computational scans of the M-N distance potentials for CH₃SiCl₃–NH₃ and CH₃GeCl₃–NH₃, both in the gas phase and bulk dielectric media, reveal a great deal of anharmonicity and a propensity for condensed-phase structural change.     

An absolute and relative rate study of the reaction of oh radicals with dimethyl sulfide

The gas phase reaction of OH radicals with dimethyl sulfide (CH₃SCH₃, DMS) has been studied using both an absolute and a relative technique at 295 ± 2 K and a total pressure of 1 atm. The absolute rate technique of pulse radiolysis combined with kinetic spectroscopy was applied. Using this technique a rate constant of (3.5 ± 0.2) × 10^?12 cm³ molecule^?1 s^?1 was obtained. For the relative rate method, rate constants for the reaction of OH with DMS were found to increase with increasing concentrations of added NO. These results are compared with the large body of kinetic and mechanistic data previously reported in the literature.     

Absence of an abrupt phase change from polycrystalline to amorphous in silicon with deposition temperature.

Using fluctuation electron microscopy, we have observed an increase in the mesoscopic spatial fluctuations in the diffracted intensity from vapor-deposited silicon thin films as a function of substrate temperature from the amorphous to polycrystalline regimes. We interpret this increase as an increase in paracrystalline medium-range order in the sample. A paracrystal consists of topologically crystalline grains in a disordered matrix; in this model the increase in ordering is caused by an increase in the grain size or density. Our observations are counter to the previous belief that the amorphous to polycrystalline transition is a discontinuous disorder-order phase transition.     

Vectorial Approach to Fast Correlation Attacks

A new, vectorial approach to fast correlation attacks on binary memoryless combiners is proposed. Instead of individual input sequences or their linear combinations, the new attack is targeting subsets of input sequences as a whole thus exploiting the full correlation between the chosen subset and the output sequence. In particular, the set of all the input sequences can be chosen as the target. The attack is based on a novel iterative probabilistic algorithm which is also applicable to general memoryless combiners over finite fields or finite rings. To illustrate the effectiveness of the introduced approach, experimental results obtained for random balanced combining functions are presentedMost of this work was done while he was with Rome CryptoDesign Center, Gemplus, Italy     

V centers in KBr

One of the major products of radiation damage in the range 120 K < T < 200 K is the D₃ center. Many effects previously associated with the V₄ center are more properly due to the D₃ center in conjunction with a center peaking at 280 nm. All results observed are consistent with the model of the D₃ center proposed by Itoh and Ikeya[7], an X₃⁻² trihalide molecule ion oriented in a 〈100〉 direction.     

On the Motion of a Dynamic System with Minimal Dissipation

The motion of a holonomic scleronomic non-conservative mechanicalsystem with minimal dissipation is considered. As applicationsof the theory several problems are studied in detail.     

Fusion around the barrier for 7Li+12C

Fusion cross-sections for the ⁷Li + ¹²C reaction have been measured at energies above the Coulomb barrier by the direct detection of evaporation residues. The heavy evaporation residues with energies below 3 MeV could not be separated out from the α-particles in the spectrum and hence their contribution was estimated using statistical model calculations. The present work indicates that suppression of fusion cross-sections due to the breakup of ⁷Li may not be significant for ⁷Li + ¹²C reaction at energies around the barrier.