Genuine binding energy of the hydrated electron.

The unknown influence of inelastic and elastic scattering of slow electrons in water has made it difficult to clarify the role of the solvated electron in radiation chemistry and biology. We combine accurate scattering simulations with experimental photoemission spectroscopy of the hydrated electron in a liquid water microjet, with the aim of resolving ambiguities regarding the influence of electron scattering on binding energy spectra, photoelectron angular distributions, and probing depths. The scattering parameters used in the simulations are retrieved from independent photoemission experiments of water droplets.

Solvated Electrons in Clusters: Magic Numbers for the Photoelectron Anisotropy.

This paper reports on a curiosity concerning magic numbers in neutral molecular clusters, namely on magic numbers related to the photoelectron anisotropy in angle-resolved photoelectron spectra. With a combination of density functional calculations and experiment, we search for magic numbers in Na(H2O)n, Na(NH3)n, Na(CH3OH)n, and Na(CH3OCH3)n clusters. In clusters of high symmetry, the highest occupied molecular orbital can be delocalized over an extended region, forming a symmetric charge distribution of high s character, which results in a pronounced anisotropy in the photoelectron angular distribution.

Angle-Resolved Photoemission of Solvated Electrons in Sodium-Doped Clusters.

Angle-resolved photoelectron spectroscopy of the unpaired electron in sodium-doped water, methanol, ammonia, and dimethyl ether clusters is presented. The experimental observations and the complementary calculations are consistent with surface electrons for the cluster size range studied. Evidence against internally solvated electrons is provided by the photoelectron angular distribution.

Global analytical potential energy surface for the electronic ground state of NH3 from high level ab initio calculations.

The analytical, full-dimensional, and global representation of the potential energy surface of NH(3) in the lowest adiabatic electronic state developed previously (Marquardt, R.; et al. J.

Photoionization of small sodium-doped acetic acid clusters.

The uptake of sodium and the fragmentation before and after "soft" photoionization with ultraviolet light are investigated for small acetic acid clusters. The acetic acid clusters are generated in a supersonic expansion and ionized with ultraviolet light after doping with sodium in a pick-up chamber. The composition of the bare acetic acid clusters in the molecular beam is determined independently from complementary photoionization experiments using extreme ultraviolet light.

Hydrogen exchange in formic acid dimer: tunnelling above the barrier.

The Raman spectrum of formic acid dimer in the OH stretch fundamental range is analysed in terms of a fully coupled vibrational Hamiltonian for the seven most important in-plane degrees of freedom involved in the hydrogen exchange process. The Raman spectrum calculated with potential and polarizability functions obtained from density functional theory reproduces the observed band structure. Wavepacket calculations reveal a remarkably slow hydrogen exchange on the timescale of several ps even at excess energies in the range of 10-15 kJ mol(-1).

PFI-ZEKE photoelectron spectrum of CH2F2, ionisation potential and ionic fragmentation appearance potentials.

The first vibrationally resolved pulsed-field-ionisation zero-kinetic-energy (PFI-ZEKE) photoelectron spectrum of difluoromethane from its adiabatic ionisation potential (formation of the C(2v) conformer of CH(2)F(2)(+)) to the onset of the first ionic fragmentation channel is presented. Precise values for the adiabatic ionisation potential (12.7252 +/- 0.

Adiabatic ionization potential of acetic acid and torsional dynamics of its cation.

Pulsed-field-ionization zero-kinetic-energy photoelectron spectroscopy and supersonic cooling are used to investigate the CH(3) torsional dynamics of the acetic acid cation and to determine an accurate value for the first adiabatic ionization potential of acetic acid (IP=85 912+/-5 cm(-1)), which has been the subject of debates for more than 40 yr. A doubling of the torsional barrier upon ionization is due to a significant shortening of the C-C bond and reduces the tunneling efficiency by an order of magnitude.

Large curvature tunnelling on the reaction path.

The reaction path Hamiltonian [J. Chem. Phys.

Phase, shape, and architecture of SF6 and SF6/CO2 aerosol particles: infrared spectra and modeling of vibrational excitons.

Information on the phase, shape, and architecture of pure SF(6) and mixed SF(6)/CO(2) aerosol particles is extracted from experimental infrared spectra by comparison with predictions from quantum mechanical exciton calculations. The radius of the particles lies around 50 nm. The following extensions to our previous vibrational exciton model are included: (i) To account for the many degrees of freedom of degenerate vibrational bands of aerosol particles, we take a time-dependent approach to calculate infrared absorption spectra directly from the dipole autocorrelation function.

Size effects in the infrared spectra of NH3 ice nanoparticles studied by a combined molecular dynamics and vibrational exciton approach.

Infrared extinction spectra of ammonia ice nanoparticles with radii between 2 and 10 nm show pronounced band shape variations depending on the conditions of particle formation by collisional cooling. We present experimental and theoretical evidence showing that the variations in the region of the nu2 (umbrella) fundamental are due to changes in the particle size. The effect is analyzed in terms of an explicit atomistic model of the particles' structure and vibrational dynamics.

Concerted hydrogen exchange tunneling in formic acid dimer.

The effect of conformational relaxation on the quantum dynamics of the hydrogen exchange tunneling is studied in the D2h subspace of formic acid dimer. The fully coupled quantum dynamics in up to six dimensions are derived for potential energy hypersurfaces interpolated directly from hybrid density functional calculations with and without geometry relaxation. For a calculated electronic barrier height of 35.