Description: This article discusses calculations that predict a large inverse H/D kinetic isotope effect. Abstract: Tunneling rates are expected to decrease exponentially with the square root of the effective tunneling mass. Therefore, on substitution of a heavier for a lighter isotope, the observation of a large kinetic isotope effect (KIE), involving a substantial decrease in rate constant, is a commonly used diagnostic for a large contribution from quantum mechanical tunneling to a reaction. However, in this communication, the authors report the results of calculations that make the opposite prediction about some of the KIEs on the ring opening of cyclopropylcarbinyl radical (1) to 3-butene-1-y1 radical (2) by tunneling at cryogenic temperatures. Substitution of a heavier for a lighter isotope at the radical center (C1) of 1 is calculated to accelerate the rate of tunneling, giving KIEs at this carbon that are inverse. Of particular note is the authors' prediction that substitution of deuterium for both hydrogens at C1 will lead to a nearly 3-fold increase in the rate of reaction at temperatures so low that ring opening proceeds exclusively by tunneling from the lowest vibrational level.

Description: This article discusses canonical and noncanonical equilibrium distribution. Abstract: We address the problem of the dynamical foundation of noncanonical equilibrium. We consider, as a source of divergence from ordinary statistical mechanics, the breakdown of the condition of time scale separation between microscopic and macroscopic dynamics. We show that this breakdown has the effect of producing a significant deviation from the canonical prescription. We also show that, while the canonical equilibrium can be reached with no apparent dependence on dynamics, the specific form of noncanonical equilibrium is, in fact, determined by dynamics. We consider the special case where the thermal reservoir driving the system of interest to equilibrium is a generator of intermittent fluctuations. We assess the form of the noncanonical equilibrium reached by the system in this case. Using both theoretical and numerical arguments we demonstrate that Lévy statistics are the best description of the dynamics and that the Lévy distribution is the correct basin of attraction. We show that the correct path to noncanonical equilibrium by means of strictly thermodynamic arguments has not yet been found, and that further research has to be done to establish a connection between dynamics and thermodynamics.

Description: This article discusses carbon K-shell x-ray and Auger-electron production in hydrocarbons and carbon oxides by 0.6-2.0-MeV protons. Abstract: Carbon K-shell x-ray and Auger-electron-production cross sections are reported for 0.6-2.0-MeV protons incident on CH4 (methane), C2H2 (acetylene), n-C4H10 (normal butane), i-C4H10 (isobutane), C6H6 (benzene), CO, and CO2. A variable-geometry end-window proportional counter with an alternative procedure for the determination of its transmission was used in collection of the x-ray data. A constant-energy-mode π/4 parallel-plate electrostatic analyzer served in the detection of Auger electrons. K-shell Auger-electron-production cross sections are compared with the predictions of the first Born theory and the perturbed-stationary-state theory which accounts for energy-loss, Coulomb deflection, and relativistic effects (ECPSSR). These data show fair agreement with the ECPSSR theory when the chemical shifts, of the carbon K-shell binding energy in molecules, are included in the calculations. This agreement is even better after effects of intramolecular scattering are considered. Validity of the geometrical model by Matthews and Hopkins [Phys. Rev. Lett. 40, 1326(1978)] is established after a scrutiny of the inelastic cross sections for scattering of Auger-electrons within the molecule and their effective dislocation out of the detector's window. The x-ray cross sections show particularly strong variations with the target molecular ...

Description: This article discusses cardiac and metabolic physiology of early larval zebrafish (Danio rerio) reflecting parental swimming stamina. Abstract: Swimming stamina in adult fish is heritable, it is unknown if inherited traits that support enhanced swimming stamina in offspring appear only in juveniles and/or adults, or if these traits actually appear earlier in the morphologically quite different larvae. To answer this question, mature adult zebrafish (Danio rerio) were subjected to a swimming performance test that allowed separation into low swimming stamina or high swimming stamina groups. Adults were then bred within their own performance groups. Larval offspring from each of the two groups, designated high (L(HSD)) and low stamina-derived larvae (L(LSD)), were then reared at 27°C in aerated water (21% O(2)). Routine (f(H),r) and active (f(H),a) heart rate, and routine [Formula: see text] and active [Formula: see text] mass-specific oxygen consumption were recorded from 5 days post fertilization (dpf) through 21 dpf, and gross cost of transport and factorial aerobic metabolic scope were derived from [Formula: see text] measurements. Heart rate generally ranged between 150 and 225 bpm in both L(HSD) and L(LSD) populations. However, significant (P<0.05) differences existed between the L(LSD) and L(HSD) populations at 5 and 14 dpf in ...

Description: This article discusses carrier-envelope phase effect on atomic excitation by few-cycle rf pulses. Abstract: We present an experimental and theoretical study of the carrier-envelope phase effects on population transfer between two bound atomic states interacting with intense ultrashort pulses. Radio frequency pulses are used to transfer population among the ground state hyperfine levels in rubidium atoms. These pulses are only a few cycles in duration and have Rabi frequencies of the order of the carrier frequency. The phase difference between the carrier and the envelope of the pulses has a significant effect on the excitation of atomic coherence and population transfer. The authors provide a theoretical description of this phenomenon using density matrix equations. The authors discuss the implications and possible applications of their results.