Comparison between experimental and calculated results on the decomposition of chemically activated alcohols

The life times of chemically activated alcohols have been determined using the high-pressure unimolecular rate parameters for thermal decomposition of alcohols from shocktube studies and RRKM calculations. They are compared with literature numbers (from insertion of 0(¹D) into hydrocarbons). It is suggested that in some cases singlet oxygen carries excess energy into the hydrocarbon. The consequences of such an assumption are explored and discrepancies with previously published conclusions discussed.     

Thermal decomposition of 3,4-dimethylpentene-1, 2,3,3-trimethylpentane, 3,3-dimethylpentane,and isobutylbenzene in a single pulse shock tube

Several hydrocarbons have been pyrolyzed in a single pulse shock tube. Rate parameters for the main bond breaking step have been found to be In combination with similar studies carried out earlier and through application of the well-established experimental rule (k(AB)/k_r(AA)k_r(BB))^1/2 ～ 2 where A and B are radicals and the rate constants are for the combination of these radicals, rate parameters for the thermal decomposition of all the hydrocarbons formed from any pair of the following radicals: methyl, ethyl, isopropyl, t-butyl, t-amyl, allyl, methylallyl, and benzyl have been calculated. The available calculated and experimental values of the decomposition rate constants are in excellent agreement. It appears that, with the possible exception of reactions involving the ejection of methyl radicals, the frequency factors per bond are nearly constant, depending only upon the type of carbon–carbon bond that is being broken. These values are all lower than those expected from the radical recombination rates. Heats of formation of ethyl, t-amyl, benzyl, methylallyl, n-propyl, s-butyl, isobutyl, neopentyl, and 3-pentyl radicals have been derived. Rate parameters for the decomposition of some simple ketones and ethers have also been estimated.     

Raman spectroscopy of intercalated layered structure compounds

The Raman spectra of intercalated 1TTaS₂ and 2HTaSe₂ have been measured for the first time. Normal symmetry allowed optic phonons and charge density wave induced modes are observed in both systems. The spectra of the ethylenediamine intercalated compounds are qualitatively similar to those of the pure materials with small quantitative shifts in frequency and changes in the relative intensities of the CDW induced modes. The qualitative similarities in the spectra of the pure and the intercalated compounds reflect the two dimensional character of these materials and show that the dynamic properties of the charge density wave states are largely determined by intralayer effects.     

Thermal stability of intermediate sized acetylenic compounds and the heats of formation of propargyl radicals

4-Methylhexyne-1, 5-methylhexyne-1, hexyne-1, and 6-methylheptyne-2 have been decomposed in comparative-rate single-pulse shock-tube experiments. Rate expressions for the initial decomposition reactions at 1100°K and from 2 to 6 atm pressure are In combination with previous results, rate expressions for propargyl C? C bond cleavage are related to that for the alkanes by the expression These results yield a propargyl resonance energy of D(nC₃H₇-H) – D(C₃H₃-H) = 36 ± 2 kJ, in excellent agreement with a previous shock-tube study. They also lead to D(CH₃C≡CCH₂-H) – D(C₃H₃-H) = 0.6 ± 3 kJ, D(sC₄H₉-H) – D(iC₃H₇-H) = 0 ± 3 kJ, D(iC₄H₉-H) – D(nC₃H₇-H) = 2 ± 3 kJ, and D(nC₃H₇-H) – D(iC₃H₇-H) = 13.9 ± 3 kJ (all values are for 300°K). The systematics of the molecular decomposition process are explored.     

A convolution approximation for Van Hove correlation function in liquids

The relative motions of particles in a simple liquid may be described as one-dimensional radial diffusion in an effective potential of the mean force. This effective potential may be obtained by an iteration procedure with the Vineyard approximation as the initial step. Using a harmonic approximation for the potential, the “distinct” part of the Van Hove time-dependent correlation function is then the convolution of a modified radial distribution function with a modified self-correlation function. The former describes the average positions of particles whereas the latter describes the density profile around the average position. For liquid argon, this modified convolution procedure appears to give results in satisfactory agreement with molecular dynamics.     

The dependence of inelastic electron tunneling on junction roughness

We have made a series of Al-Al₂O₃-benzoic acid-Pb inelastic electron tunneling spectroscopy (IETS) junctions on substrates roughened by varying thicknesses of CaF₂. The vibrational peaks due to the molecular monolayer of benzoic acid disappear as the substrates are made rougher. We speculate on the cause of this disappearance.     

XPS studies of ion-bombardment damage of transition metal sulfides

Radiation damage to the surface of transition metal sulfides under ～1-keV ion bombardment has been investigated by photoelectron spectroscopy. Under     

Efficient calculation of electron diffraction for the structural determination of nanomaterials

A critical advance in the technique of low-energy electron diffraction is presented and shown to enable determining detailed structures of nanomaterials, based on experimental methods that already exist or have been proposed. Our new cluster approach speeds up the computation to scale as n logn, rather than the current n3 or n2, with n the number of atoms, for example. Applications are illustrated for C60 molecules adsorbed on a Cu(111) surface, with and without coadsorbed metal atoms, exhibiting sensitivity to important structural features such as buckyball size and deformation.