Virtual state scattering with cold electrons: para-xylene and para-difluorobenzene

The scattering of electrons with kinetic energies down to a few meV by para-xylene and para-difluorobenzene has been observed experimentally with an electron beam energy resolution of 0.95 to 1.5 meV (full width half maximum). At low electron energies the collisions can be considered as cold scattering events because the de Broglie wavelength of the electron is considerably larger than the target dimensions. The scattering cross sections measured rise rapidly at low energy due to virtual state scattering. The nature of this scattering process is discussed using s- and p-wave phase shifts derived from the experimental data. Scattering lengths are derived of, respectively, -9.5+/-0.5 and -8.0+/-0.5 a.u. for para-xylene and para-difluorobenzene. The virtual state effect is interpreted in terms of nuclear diabatic and partially adiabatic models, involving the electronic and vibronic symmetries of the unoccupied orbitals in the target species. The concept of direct and indirect virtual state scattering is introduced, through which the present species, in common with carbon dioxide and benzene, scatter through an indirect virtual state process, whereas other species, such as perfluorobenzene, scatter through a direct process. (C) 2005 American Institute of Physics.

The closed orbits and the photo-excitation scaled spectrum of the hydrogen atom in crossed fields

In a recent Letter to the Editor (J Rao, D Delande and K T Taylor 2001 J. Phys. B: At. Mol. Opt. Phys. 34 L391-9) we made a brief first report of our quantal and classical calculations for the hydrogen atom in crossed electric and magnetic fields at constant scaled energy and constant scaled electric field strength. A principal point of that communication was our statement that each and every peak in the Fourier transform of the scaled quantum photo-excitation spectrum for scaled energy value epsilon = -0.586 538 871028 43 and scaled electric value (f) over tilde = 0.068 537 846 207 618 71 could be identified with a scaled action value of a found and mapped-out closed orbit up to a scaled action of 20. In this follow-up paper, besides presenting full details of our quantum and classical methods, we set out the scaled action values of all 317 closed orbits involved, together with the geometries of many.

Single- and multiphoton detachment of K

Single- and multiphoton detachment rates have been calculated for K- using the R-matrix Floquet approach. Single-photon detachment rates, obtained at a laser field peak intensity of 10(9) W cm(-2), are discussed and compared with other theoretical work. Two-photon detachment rates at the same intensity have also been obtained, and similarities with results from earlier calculations for Li- and Na- are discussed. Three-photon rates are also presented at this laser intensity, and are compared and contrasted with those arising in the single-photon case, since both involve resonance structure with P-1(o) symmetry. The influence of resonances such as the 5s(2) S-1(e) doubly excited state and excitations of the residual atom are also considered.

Restricted rotation dynamics and far-infrared spectra of liquid water governed by elastic interactions

A semi-phenomenological model describing wideband dielectric and far-infrared spectra of liquid water was proposed recently by the same authors [J. Mol. Struct. 606 (2002) 9], where a small dipole-moment component changing harmonically with time determines a weak absorption band (termed here the R-band) centred at the wavenumber v similar to 200 cm(-1). In the present work, a rough molecular theory of the R-band based on the concept of elastic interactions is given. Stretching and bending of hydrogen bonds cause restricted rotation (RR) of a polar water molecule in terms of a dimer comprising the H- bonded molecules. Analytical expression for the RR frequency nu(str) is derived as a function of the RR amplitude, geometrical parameters and force constants. The density g(nu(str)) of frequency distribution is shown to be centred in the R-band. The spectrum of the dipolar auto-correlation function calculated for this structural-dynamical model is found. A composite model comprising two intermolecular potentials is proposed, which yields for water a good description of the experimental wideband (from 0 to 1000 cm(- 1)) spectra of complex permittivity and of absorption coefficient. The presented interpretation of these spectra is based on a concept that water presents a two-component solution, with components differing by the types of molecular rotation. (C) 2003 Elsevier B.V. All rights reserved.

Parity nonconservation in electron recombination of multiply charged ions

We discuss a parity nonconserving asymmetry in the cross section of KLL dielectronic recombination of polarized electrons on the hydrogenlike ions with Z less than or similar to 60. This effect is strongly enhanced because of the near degeneracy of doubly excited 2l2l(') states of opposite parity in He-like ions. For ions with Z similar to 30 the asymmetry is of the order of 10(-9). For Z approximate to 48 a level crossing takes place, leading to the PNC asymmetry of -1.3x10(-8), which is 10(8) times greater than the basic strength of the weak interaction in atoms.

Ultrafast ionization study of N-2 in intense linearly and circularly polarized laser fields

A detailed investigation has been carried out of N-2 molecules in intense 55 and 220 fs, linear and circular polarized, 790 nm laser pulses. Using an intensity selective scanning technique, ionization, dissociation, and dissociative ionization channels have been studied. Remarkably similar enhancements of signal with linear polarization observed for double ionization and dissociation channels demonstrate the dominance of dynamic alignment over rescattering effects. Fragmentation energies from dissociative ionization are reasonably well reproduced by classical trajectory calculations, the higher charged fragments displaying evidence of post dissociative ionization.

Experimental investigation of the processes determining x-ray emission intensities from charge-exchange collisions

Absolute cross sections have been measured for single and double charge exchange and x-ray line emission for highly charged ions of C, N, 0, and Ne colliding with He, H-2 CO2, and H2O at collisions energies of 7q keV. Present results of charge exchange in He and H-2 compare favorably with previous results. For CO2 and H2O, where prior work is scarce, the classical overbarrier model is found to overestimate results by up to a factor of 3. An analysis of the relative intensities of the observed Lyman x-ray transitions indicates that capture into l states is not statistical, as collision velocities are insufficient to populate the highest angular-momentum states. The importance of autoionization following multiple capture is highlighted, and enhanced radiative stabilization following double capture is observed and compared to other studies. Present results are also discussed in terms of mechanisms likely to generate x-ray emission in comets.

An isothermal-isobaric Langevin thermostat for simulating nanoparticles under pressure: Application to Au clusters

We present a method for simulating clusters or, molecules subjected to an external pressure, which is exerted by a pressure-transmitting medium. It is based on the canoninical Langevin thermostat, but extended in such a way that the Brownian forces are allowed to operate only from the region exterior to the cluster. We show that the frictional force of the Langevin thermostat is linked to the pressure of the reservoir in a unique way, and that this property manifests itself when the particle it acts upon is not pointlike but has finite dimensions. By choosing appropriately the strength of the random forces and the friction coefficient, both temperature and pressure can be controlled independently. We illustrate the capabilities of this new method by calculating the compressibility of small gold clusters under pressure.

Multiple proton translocation in biomolecular systems: concerted to stepwise transition in a simple model

In this paper we study a simple model potential energy surface (PES) useful for describing multiple proton translocation mechanisms. The approach presented is relevant to the study of more complex biomolecular systems like enzymes. In this model, at low temperatures, proton tunnelling favours a concerted proton transport mechanism, while at higher temperatures there is a crossover from concerted to stepwise mechanisms; the crossover temperature depends on the energetic features of the PES. We illustrate these ideas by calculating the crossover temperature using energies taken from ab initio calculations on specific systems. Interestingly, typical crossover temperatures lie around room temperature; thus both concerted and stepwise reaction mechanisms should play an important role in biological systems, and one can be easily turned into another by external means such as modifying the temperature or the pH, thus establishing a general mechanism for modulation of the biomolecular function by external effectors.

A Maxwell relation for current-induced forces

A Maxwell relation is presented involving current-induced forces. It provides a new physical picture of the origin of current-induced forces and in the small-voltage limit it enables the identification of a simple thermodynamic potential which drives electromigration. The question of whether current-induced forces are conservative or non-conservative is discussed briefly in the light of these insights.