a b s t r a c tArrhenius plots, which are used to represent the effects of temperature on the rates of chemical and biophysical processes and on various transport phenomena in materials science, may exhibit deviations from linearity. Account of curvature is provided here by a formula which involves a deformation of the exponential function, of the kind recently encountered in treatments of non-extensivity in statistical mechanics. We present here examples on diverse topics -respiration rates of plants, speed of gliding of bacteria, quantum mechanical tunneling in a chemical reaction -illustrating the variety of possible applications and the additional insight that can be gained.

Production, characterization and control of polarization states of molecules (specifically, alignment and/or orientation) are of importance for investigating in detail the stereodynamics of elementary processes involving elastic, inelastic and reactive events and also to prepare targets for selective photodynamical investigations. The focus here is on those molecular beam techniques which show perspectives in the applications offering appealing features for "duty cycle" and intensity characteristics. After a review of the basic experimental advances, mainly obtained in the last ten years, the attention will be addressed to recent studies carried out on the collisional alignment of hydrocarbon molecules and on orientation of symmetric top molecules by exploiting honeycomb hexapole fields. The first case is a prototype of "natural" polarization techniques, the second one of those where polarization is "forced" by external fields.

The exploration of alternative roads that open to molecules with sufficient energy to yield different products permits prediction and eventually control of the outcomes of chemical reactions. Advanced imaging techniques for monitoring laser-induced photodissociation are here combined with dynamical simulations, involving ample sets of classical trajectories generated on a quantum chemical potential energy surface. Methyl formate, HCOOCH3, is photodissociated at energies near the triple fragmentation threshold into H, CO and OCH3. Images of velocity and rotational distributions of CO exhibit signatures of alternative routes, such as those recently designated as transition-state vs. roaming-mediated. Furthermore, a demonstration of the triple fragmentation route is given, and also confirmed by H-atom product imaging and FTIR time-resolved spectra of the intermediate HCO radical. In addition, the relevance of nonadiabatic transitions promoted by a conical intersection is clarified by simulations as the privileged "reactivity funnel" of organic photochemistry, whereby the outcomes of molecular photoexcitation are delivered to electronic ground states.

Steric effect for N2(C,3Piu) formation in the energy transfer reaction of Ar(3P2)+N2 was directly measured by using an oriented Ar(3P2,MJ=2) beam at a collision energy of 0.06 eV. The N2(C,3Piu) chemiluminescence intensity was measured as a function of the magnetic orientation field direction in the collision frame. A significant alignment effect on the energy transfer probability was observed. The relative reactivity for each magnetic substate in the collision frame sigma|MJ'|was determined to be sigma|2|:sigma|1|:sigma(0)=0.50:0.60:1.00. It is suggested that the observed steric effect is primarily due to the favorable configuration of the 3p orbital for the efficient overlap with the 2sigma(u) molecular orbital of N(2).