Autoionization

Abstract: The dissociation of a water molecule in liquid water is the fundamental event in acid-base chemistry, determining the pH of water. Because of the short time scales and microscopic length scales involved, the dynamics of this autoionization have not been directly probed by experiment. Here, the autoionization mechanism is revealed by sampling and analyzing ab initio molecular dynamics trajectories. We identify the rare fluctuations in solvation energies that destabilize an oxygen-hydrogen bond. Through the transfer of protons along a hydrogen bond "wire," the nascent ions separate by three or more neighbors. If the hydrogen bond wire connecting the two ions is subsequently broken, a metastable charge-separated state is visited. The ions may then diffuse to large separations. If, however, the hydrogen bond wire remains unbroken, the ions recombine rapidly. Because of their concomitant large electric fields, the transient ionic species produced in this case may provide an experimentally detectable signal of the dynamics we report.

Abstract: The paper presents new calculations of ionization equilibrium fractions of 11 abundant elements (C, N, O, Ne, Mg, Si, S, Ar, Ca, Fe, Ni) as functions of temperature. Convenient coefficients for fitting the rates of collisional ionization, radiative recombination, and dielectronic recombination are also tabulated. Many of the ionization rates are based on recent experimental measurements of cross sections for collisional ionization and autoionization following inner-shell excitation. These rates are used elsewhere in computations of nonequilibrium ionization, radiative cooling, radiative shock models, and plasma emission diagnostics.

Abstract: Autoionization of argon atoms was studied experimentally by transient absorption spectroscopy with isolated attosecond pulses. The peak position, intensity, linewidth, and shape of the $3s3{p}^{6}np$ $^{1}P$ Fano resonance series (26.6--29.2 eV) were modified by intense few-cycle near infrared laser pulses, while the delay between the attosecond pulse and the laser pulse was changed by a few femtoseconds. Numerical simulations revealed that the experimentally observed splitting of the $3s3{p}^{6}4p$ $^{1}P$ line is caused by the coupling between two short-lived highly excited states in the strong laser field.