A nonlinear time-dependent two-temperature collisional-radiative model for air plasma has been developed for pressures between 1kPa and atmospheric pressure to be applied to the flow conditions of space vehicle re-entry into the Earth’s atmosphere. The model consists of 13 species: N2, O2, N, O, NO, N2+, O2+, N+, O+, NO+, O2−, O− in their ground state and major electronic excited states and of electrons. Many elementary processes are considered given the temperatures involved (up to 10 000K). Time scales to reach the final nonequilibrium or equilibrium steady states are derived. Then we apply our model to two typical re-entry situations and show that O2− and O− play an important role during the ionization phase. Finally, a comparison with existing reduced kinetic mechanisms puts forward significant discrepancies for high velocity flows when the flow is in chemical nonequilibrium and smaller discrepancies when the flow is close to chemical equilibrium. This comparison illustrates the interest of using a time-dependent collisional-radiative model to validate reduced kinetic schemes for the relevant time scales of the flows studied.

pKa's, proton affinities, and proton dissociation free energies characterize numerous properties of drugs and the antioxidant activity of some chemical compounds. Even with a higher computational level of theory, the uncertainty in the proton solvation free energy limits the accuracy of these parameters. We investigated the thermochemistry of the solvation of the proton in methanol within the cluster-continuum model. The scheme used involves up to nine explicit methanol molecules, using the IEF-PCM and the strategy based on thermodynamic cycles. All computations were performed at B3LYP/6-31++G(dp) and M062X/6-31++G(dp) levels of theory. It comes out from our calculations that the functional M062X is better than B3LYP, on the evaluation of gas phase clustering energies of protonated methanol clusters, per methanol stabilization of neutral methanol clusters and solvation energies of the proton in methanol. The solvation free energy and enthalpy of the proton in methanol were obtained after converging the partial solvation free energy of the proton in methanol and the clustering free energy of protonated methanol clusters, as the cluster size increases. Finally, the recommended values for the solvation free energy and enthalpy of the proton in methanol are -257 and -252 kcal/mol, respectively.

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The accurate evaluation of pKa's, or solvation energies of the proton in methanol at a given temperature is subject to the determination of the most favored structures of various isomers of protonated (H(+)(MeOH)n) and neutral ((MeOH)n) methanol clusters in the gas phase and in methanol at that temperature. Solvation energies of the proton in a given medium, at a given temperature may help in the determination of proton affinities and proton dissociation energies related to the deprotonation process in that medium and at that temperature. pKa's are related to numerous properties of drugs. In this work, we were interested in the determination of the most favored structures of various isomers of protonated methanol clusters in the gas phase and in methanol, at a given temperature. For this aim, the M062X/6-31++G(d,p) and B3LYP/6-31++G(d,p) levels of theory were used to perform geometries optimizations and frequency calculations on various isomers of (H(+)(MeOH)n) in both phases. Thermal effects were retrieved using our homemade FORTRAN code. Thus, we accessed the relative populations of various isomers of protonated methanol clusters, in both phases for temperatures ranging from 0 to 400 K. As results, in the gas phase, linear structures are entropically more favorable at high temperatures, while more compact ones are energetically more favorable at lower temperatures. The trend is somewhat different when bulk effects are taken into account. At high temperatures, the linear structure only dominates the population for n ≤ 6, while it is dominated by the cyclic structure for larger cluster sizes. At lower temperatures, compact structures still dominate the population, but with an order different from the one established in the gas phase. Hence, temperature effects dominate solvent effects in small cluster sizes (n ≤ 6), while the reverse trend is noted for larger cluster sizes.

A series of computations based on multichannel quantum defect theory have been performed in order to produce the cross sections of rotational transitions (excitationsto 10) and of their competitive process, the dissociative recombination, induced by collisions of HD + ions with electrons in the energy range 10 −5 to 0.3 eV. Maxwell anisotropic rate coefficients, obtained from these cross sections in the conditions of the Heidelberg Test Storage Ring (TSR) experiments (k B T t = 2.8 meV and k B T l = 45 μeV), have been reported for those processes in the same electronic energy range. Maxwell isotropic rate coefficients have been presented as well for electronic temperatures up to a few hundred Kelvins. Very good overall agreement is found between our results for rotational transitions and the former theoretical computations as well as with experiment. Furthermore, due to the full rotational computations performed, the accuracy of the resulting dissociative recombination cross sections is improved considerably.

The non-relativistic static and dynamic dipole polarizabilities of a hydrogen atom experiencing a cylindrical confinement are investigated. Two methods based on B-splines are used for computations of energies and wavefunctions. The first method is a variational-based method while the second one proceeds by a fit of the non-separable Coulomb potential in the product form. The computed energies compare very well with previous computations. They converge, as well as the dipole polarizability, to the exact unconfined free atom values with increasing basis size. The fit approach is found to be advantageous, as it helps to reduce the computational time without loss of accuracy.

The collision-energy resolved rate coefficient for dissociative recombination of HD + ions in the vibrational ground state is measured using the photocathode electron target at the heavy-ion storage ring TSR. Rydberg resonances associated with ro-vibrational excitation of the HD + core are scanned as a function of the electron collision energy with an instrumental broadening below 1 meV in the low-energy limit. The measurement is compared to calculations using multichannel quantum defect theory, accounting for rotational structure and interactions and considering the six lowest rotational energy levels as initial ionic states. Using thermal equilibrium level populations at 300 K to approximate the experimental conditions, close correspondence between calculated and measured structures is found up to the first vibrational excitation threshold of the cations near 0.24 eV. Detailed assignments, including naturally broadened and overlapping Rydberg resonances, are performed for all structures up to 0.024 eV. Resonances from purely rotational excitation of the ion core are found to have similar strengths as those involving vibrational excitation. A dominant low-energy resonance is assigned to contributions from excited rotational states only. The results indicate strong modifications in the energy dependence of the dissociative recombination rate coefficient through the rotational excitation of the parent ions, and underline the need for studies with rotationally cold species to obtain results reflecting low-temperature ionized media.

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