UV continuum emission and diagnostics of hydrogen-containing non-equilibrium plasmas

For the first time the emission of the radiative dissociation continuum of the hydrogen molecule ($a^{3}\Sigma_{g}^{+} \to b^{3}\Sigma_{u}^{+}$ electronic transition) is proposed to be used as a source of information for the spectroscopic diagnostics of non-equilibrium plasmas. The detailed analysis of excitation-deactivation kinetics, rate constants of various collisional and radiative transitions and fitting procedures made it possible to develop two new methods of diagnostics of: (1) the ground $X^{1}\Sigma_{g}^{+}$ state vibrational temperature $T_{\text{vib}}$ from the relative intensity distribution, and (2) the rate of electron impact dissociation (d[\mbox{H_{2}}]/dt)_{\text{diss}} from the absolute intensity of the continuum. A known method of determination of $T_{\text{vib}}$ from relative intensities of Fulcher-$\alpha$ bands was seriously corrected and simplified due to the revision of $d \to a$ transition probabilities and cross sections of $d \gets X$ electron impact excitation. General considerations are illustrated with examples of experiments in pure hydrogen capillary-arc and H$_{2}$+Ar microwave discharges.Comment: REVTeX, 25 pages + 12 figures + 9 tables. Phys. Rev. E, eprint replaced because of resubmission to journal after referee's 2nd repor

Quantum dynamics in strong fluctuating fields

A large number of multifaceted quantum transport processes in molecular systems and physical nanosystems can be treated in terms of quantum relaxation processes which couple to one or several fluctuating environments. A thermal equilibrium environment can conveniently be modelled by a thermal bath of harmonic oscillators. An archetype situation provides a two-state dissipative quantum dynamics, commonly known under the label of a spin-boson dynamics. An interesting and nontrivial physical situation emerges, however, when the quantum dynamics evolves far away from thermal equilibrium. This occurs, for example, when a charge transferring medium possesses nonequilibrium degrees of freedom, or when a strong time-dependent control field is applied externally. Accordingly, certain parameters of underlying quantum subsystem acquire stochastic character. Herein, we review the general theoretical framework which is based on the method of projector operators, yielding the quantum master equations for systems that are exposed to strong external fields. This allows one to investigate on a common basis the influence of nonequilibrium fluctuations and periodic electrical fields on quantum transport processes. Most importantly, such strong fluctuating fields induce a whole variety of nonlinear and nonequilibrium phenomena. A characteristic feature of such dynamics is the absence of thermal (quantum) detailed balance.Comment: review article, Advances in Physics (2005), in pres

Hot recombination of photogenerated ion pairs

The recombination dynamics of ion pairs generated upon electron transfer quenching of perylene in the first singlet excited state by tetracyanoethylene in acetonitrile is quantitatively described by the extended unified theory of photoionization/recombination. The extension incorporates the hot recombination of the ion pair passing through the level-crossing point during its diffusive motion along the reaction coordinate down to the equilibrium state. The ultrafast hot recombination vastly reduces the yield of equilibrated ion pairs subjected to subsequent thermal charge recombination and separation into free ions. The relatively successful fit of the theory to the experimentally measured kinetics of ion accumulation/recombination and free ion yield represents a firm justification of hot recombination of about 90% of primary generated ion pairs