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Klaus Luther

Publications and source records attributed to Klaus Luther.

6 recordsLinked to original sources
PubMed2006

Falloff curves for the Reaction CH3 + O2 (+ M) --> CH3O2 (+ M) in the pressure range 2-1000 bar and the temperature range 300-700 K.

The reaction CH(3) + O(2) (+M) --> CH(3)O(2) (+M) was studied in the bath gases Ar and N(2) in a high-temperature/high-pressure flow cell at pressures ranging from 2 to 1000 bar and at temperatures between 300 and 700 K. Methyl radicals were generated by laser flash photolysis of azomethane or acetone. Methylperoxy radicals were monitored by UV absorption at 240 nm. The falloff curves of the rate constants are represented by the simplified expression k/k(infinity) approximately [x/(1 + x)]F(cent)(1/{1+[(log)(x)/)(N)(]2}) with x = k(0)/k(infinity) F(cent) approximately 0.33, and N approximately 1.47, where k(0) and k(infinity) denote the limiting low and high-pressure rate constants, respectively. At low temperatures, 300-400 K, and pressures >300 bar, a fairly abrupt increase of the rate constants beyond the values given by the falloff expressions was observed. This effect is attributed to a contribution from the radical complex mechanism as was also observed in other recombination reactions of larger radicals. Equal limiting low-pressure rate constants k(0) = [M]7 x 10(-31)(T/300 K)(-3.0) cm(6) molecule(-2) s(-1) were fitted for M = Ar and N(2) whereas limiting high-pressure rate constants k(infinity) = 2.2 x 10(-12)(T/300 K)(0.9) cm(3) molecule(-1) s(-1) were approached. These values are discussed in terms of unimolecular rate theory. It is concluded that a theoretical interpretation of the derived rate constants has to be postponed until better information of the potential energy surface is available. Preliminary theoretical evaluation suggests that there is an "anisotropy bottleneck" in the otherwise barrierless interaction potential between CH(3) and O(2).

Journal Article↗
PubMed2006

Kinetically controlled selective ionization study on the efficient collisional energy transfer in the deactivation of highly vibrationally excited trans-stilbene.

Direct measurements of the gas-phase collisional energy transfer parameters are reported for the deactivation of highly vibrationally excited trans-stilbene molecules, initially prepared with an average energy of about 40 000 cm(-1), in the bath gases argon, CO2, and n-heptane. The method of kinetically controlled selective ionization (KCSI) has been used. Complete experimental collisional transition probability density functions P(E',E) are determined, which are represented by a monoexponential form with a parametric exponent in the argument, P(E',E) proportional to exp[-{(E - E')/(C0 + C1E)}Y] (for downward collisions), well established from earlier KCSI studies. A comparison of the first moments of energy transfer rate constants, kE,1, or of resulting first moments of energy transfer, , for trans-stilbene with those for azulene and toluene clearly shows the considerably more efficient deactivation of trans-stilbene for all bath gases, presumably due to the much greater number of very low-frequency modes of trans-stilbene. However, on a relative scale this gain in deactivation rate of excited trans-stilbene is clearly collider dependent and decreases distinctly with the growing collision efficiency of the larger bath gas molecules.

Journal Article↗
PubMed2006

Pressure and temperature dependence of the recombination of p-fluorobenzyl radicals.

The rate constants of the recombination reaction of p-fluorobenzyl radicals, p-F-C6H4CH2 + p-F-C6H4CH2 (+M) --> C14H12F2 (+M), have been measured over the pressure range 0.2-800 bar and the temperature range 255-420 K. Helium, argon, and CO2 were employed as bath gases (M). At pressures below 0.9 bar in Ar and CO2, and 40 bar in He, the rate constant k1 showed no dependence on the pressure and the nature of the bath gas, clearly indicating that it had reached the limiting high-pressure value of the energy-transfer (ET) mechanism (k(1,infinity)ET). A value of k(1,infinity)ET(T) = (4.3 +/- 0.5) x 10(-11) (T/300 K)(-0.2) cm3 molecule(-1) s(-1) was determined. At pressures above about 5 bar, the k1 values in Ar and CO2 were found to gradually increase in a pressure range where according to energy-transfer mechanism, they should remain at the constant value k(1,infinity)ET. The enhancement of the recombination rate constant beyond the value k(1,infinity)ET increased in the order He < Ar < CO2, and it became more pronounced with decreasing temperature. The dependences of k1 on pressure, temperature, and the bath gas were similar to previous observations in the recombination of benzyl radicals. The effect of fluorine-substitution of the benzyl ring on k1 values is discussed. The present results confirm the significant role of radical complexes in the recombination kinetics of benzyl-type radicals in the gas-liquid transition range. The observations on a rate enhancement beyond the experimental value of k(1,infinity)ET at elevated densities up to the onset of diffusion-control are consistently explained by the kinetic contribution of a "radical-complex" mechanism which is solely based on standard van der Waals interaction between radicals and bath gases.

Journal Article↗
PubMed2005

The role of the radical-complex mechanism in the ozone recombination/dissociation reaction.

The data bases for low-pressure rate coefficients of the dissociation of O3 and the reverse recombination of O with O2 in the bath gases M=He, Ar, N2, CO2 and SF6 are carefully analyzed. At very high temperatures, the rate constants have to correspond solely to the energy transfer (ET) mechanism. On condition that this holds for Ar and N2 near 800 K, average energies transferred per collision of -DeltaE/hc=18 and 25 cm-1 are derived, respectively. Assuming an only weak temperature dependence of DeltaE as known in similar systems, rate coefficients for the ET-mechanism are extrapolated to lower temperatures and compared with the experiments. The difference between measured and extrapolated rate coefficients is attributed to the radical complex (RC) mechanism. The derived rate coefficients for the RC-mechanism are rationalized in terms of equilibrium constants for equilibria of van der Waals complexes of O (or O2) with the bath gases and with rate coefficients for oxygen abstraction from these complexes. The latter are of similar magnitude as rate coefficients for oxygen isotope exchange which provides support for the present interpretation of the reaction in terms of a superposition of RC- and ET-mechanisms. We obtained rate coefficients for the ET-mechanism of k/[Ar]=2.3x10(-34) (T/300)(-1.5) and k/[N2]=3.5x10(-34) (T/300)(-1.5) cm6 molecule-2 s-1 and rate coefficients for the RC-mechanism of k/[Ar]=1.7x10(-34) (T/300)(-3.2) and k/[N2]=2.5x10(-34) (T/300)(-3.3) cm6 molecule-2 s-1. The data bases for M=He, CO2 and SF6 are less complete and only approximate separations of RC- and ET-mechanism were possible. The consequences of the present analysis for an analysis of isotope effects in ozone recombination are emphasized.

Argon↗
PubMed2005

PECT model analysis and predictions of experimental collisional energy transfer probabilities P(E',E) and moments for azulene and biphenylene.

Experimental collisional energy transfer data from kinetically controlled selective ionization (KCSI) and ultraviolet absorption (UVA) experiments are analyzed in the framework of the partially ergodic collision theory (PECT). Collisions of azulene and biphenylene with different colliders are investigated as case studies. The downward wings of the P(E',E) energy transfer distributions obtained from the PECT model are fitted to the recently introduced "variable-shape"-exponential 3-parameter functional form of P(E',E) obtained from KCSI experiments, P(E',E) proportional, variant exp[-{(E - E')/(C(0) + C(1)E)}(Y)]. The PECT model is able to reproduce the characteristic dependence of the KCSI "shape parameter" Y on the choice of collider, the energy dependent width of the KCSI P(E',E) distributions, described by alpha(E) = C(0) + C(1)E, and the temperature dependence of the UVA data above room temperature. The statistical approach of PECT obviously captures the essence of large molecule energy transfer at chemically significant energies without the need of knowing specific features of the detailed collision dynamics. It therefore shows promise for predicting the shape of P(E',E) in master equation kernels for larger molecules.

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