Bombardment induced ion transport--part III: experimental potassium ion conductivities in poly(para-xylylene).

The bombardment induced ion transport (BIIT) technique has been employed for studying the ionic conductivity of thin poly(p-xylylene) (PPX) films. The experiment is based on bombarding a PPX film with a c.w. potassium ion beam. The transport of ions through the film - which follows the laws of electrodiffusion - is detected as a neutralization current on the backside electrode on which the film has been deposited. This backside current scales quadratically with the acceleration potential of the ion beam and inversely cubically with the thickness of the film. This confirms theoretical predictions made in part I of this mini-series (Phys. Chem. Chem. Phys., 2011, 13, 20112-20122). This characteristic is markedly different from the Ohm-like current-voltage properties of a solid electrolyte, e.g. an ion conducting glass. The diffusion coefficient for K(+) in PPX is determined to be 8.528 × 10(-16) cm(2) s(-1) at 333 K. From the temperature dependence of the diffusion coefficient we conclude that a hopping mechanism with an activation energy of 2.74 eV ± 0.18 eV is operative.

Bombardment induced ion transport. Part I: Numerical investigation of bombardment induced ion transport through glasses and membranes on the basis of the Nernst-Planck-Poisson equations.

The bombardment of condensed matter by low energy ion beams induces ion transport through the material. A general theory for bombardment induced ion transport (BIIT) based on numerical solutions of the well known Nernst-Planck-Poisson equations is presented. The theory is applicable to polymer membranes as well as ion-conducting glasses with the implementation of appropriate boundary conditions. The fundamental properties of the theory, i.e. the capability to describe the potential, the field and the concentration/charge density profile within the two classes of materials mentioned above are demonstrated. In particular, the theory is capable of describing experimental observables which will be further elaborated in part II of this miniseries.

Bombardment induced ion transport--part II. Experimental potassium ion conductivities in borosilicate glass.

A new experimental approach for measuring the ionic conductivity of solid materials is proposed. The experiment is based on bombarding an ion conducting sample with an alkali ion beam. This generates a well defined surface potential which in turn causes ion transport in the material. The ion transport is measured at the back side of the sample. The viability of the concept is demonstrated by measuring the temperature dependence of the potassium ion conductivity of a potassium borosilicate glass. The activation energy for the potassium transport is 1.04 eV ± 0.06 eV. For comparison, conductivity data obtained by impedance spectroscopy are presented, which support the bombardment induced data.

Waveform control of orientation-dependent ionization of DCl in few-cycle laser fields.

Strong few-cycle light fields with stable electric field waveforms allow controlling electrons on time scales down to the attosecond domain. We have studied the dissociative ionization of randomly oriented DCl in 5 fs light fields at 720 nm in the tunneling regime. Momentum distributions of D(+) and Cl(+) fragments were recorded via velocity-map imaging. A waveform-dependent anti-correlated directional emission of D(+) and Cl(+) fragments is observed. Comparison of our results with calculations indicates that tailoring of the light field via the carrier envelope phase permits the control over the orientation of DCl(+) and in turn the directional emission of charged fragments upon the breakup of the molecular ion.

Phase control of molecular fragmentation with a pair of femtosecond-laser pulses.

We demonstrate the control of molecular fragmentation of o-xylene (C(8)H(10)) on a femtosecond time scale in two-pulse measurements with a pair of femtosecond-laser pulses. Parent and fragment-ion yields were recorded as a function of interpulse delays, i.e., different relative phases of the excitation pulses. The experiments revealed different fragmentation mechanisms in the temporal region of direct overlapping pulses and for separated pulses. For overlapping pulses all ion yields followed the excitation intensity which oscillated as a function of interpulse delay due to the change of constructive and destructive interference of the light fields. For larger delays, in particular, the oscillations of the C(+) and CH(3) (+) fragment-ion yield showed a significant deviation from each other. The results are interpreted as a manifestation of optical phase-dependent electronic excitations mapped onto the nuclear fragmentation dynamics.

Vacuum ultraviolet pulsed-field ionization-photoelectron study of H2S in the energy range of 10-17 eV.

Vacuum ultraviolet pulsed-field ionization-photoelectron (PFI-PE) spectra of H(2)S have been recorded at PFI-PE resolutions of 0.6-1.0 meV in the energy range of 10-17 eV using high-resolution synchrotron radiation. The PFI-PE spectrum, which covers the formation of the valence electronic states H(2)S(+) (X (2)B(1), A (2)A(1), and B (2)B(2)), is compared to the recent high-resolution He I photoelectron spectra of H(2)S obtained by Baltzer et al. [Chem. Phys. 195, 403 (1995)]. In addition to the overwhelmingly dominated origin vibrational band, the PFI-PE spectrum for H(2)S(+)(X (2)B(1)) is found to exhibit weak vibrational progressions due to excitation of the combination bands in the nu(1) (+) symmetric stretching and nu(2) (+) bending modes. While the ionization energy (IE) for H(2)S(+)(X (2)B(1)) obtained here is in accord with values determined in previously laser PFI-PE measurements, the observation of a new PFI-PE band at 12.642+/-0.001 eV suggests that the IE for H(2)S(+)(A (2)A(1)) may be 0.12 eV lower than that reported in the He I study. The simulation of rotational structures resolved in PFI-PE bands shows that the formation of H(2)S(+)(X (2)B(1)) and H(2)S(+)(A (2)A(1)) from photoionization of H(2)S(X (1)A(1)) is dominated by type-C and type-B transitions, respectively. This observation is consistent with predictions of the multichannel quantum defect theory. The small changes in rotational angular momentum observed are consistent with the dominant atomiclike character of the 2b(1) and 5a(1) molecular orbitals of H(2)S. The PFI-PE measurement has revealed perturbations of the (0, 6, 0) K(+)=3 and (0, 6, 0) K(+)=4 bands of H(2)S(+)(A (2)A(1)). Interpreting that these perturbations arise from Renner-Teller interactions at energies close to the common barriers to linearity of the H(2)S(+) (X (2)B(1) and A (2)A(1)) states, we have deduced a barrier of 23,209 cm(-1) for H(2)S(+)(X (2)B(1)) and 5668 cm(-1) for H(2)S(+)(A (2)A(1)). The barrier of 23 209 cm(-1) for H(2)S(+)(X (2)B(1)) is found to be in excellent agreement with the results of previous studies. The vibrational PFI-PE bands for H(2)S(+)(B (2)B(2)) are broad, indicative of the predissociative nature of this state.

Observation of accurate ion dissociation thresholds in pulsed field ionization-photoelectron studies.

We report the first observation, together with a mechanism for such an observation, of a steplike feature in the pulsed field ionization photoelectron measurement of CH4(C2H2), marking the 0 K dissociation threshold for the formation of CH3(+) + H(C2H(+) + H) from CH4(C2H2). The nonexistence of a step in the spectrum for C 2H4 at its dissociation threshold for C2H2(+) formation provides strong support for the proposed mechanism. This experiment shows that, for a range of molecules, where the ion dissociation lifetimes near the dissociation thresholds are <10(-7) s, pulsed field ionization photoelectron measurements will yield not only highly accurate ionization energies, but also 0 K dissociation thresholds.