Rotationally resolved fluorescence-dip and ion-dip spectra of single rovibronic states of benzene

We report fluorescence-dip as well as ion-dip spectra of single rovibronic one-photon states of benzene with a linewidth as narrow as 0.14 cm'1. The selective excitation of the rovibronic states was achieved through the combination of a frequency-doubled pulsed amplified cw dye laser (Avuv 100 MHz) and a collimated molecu-lar beam. The detailed analysis of the dip spectra shows that the observed spectral features correspond to single rovibronic transitions if suitable states are excited. From the spectra, precise harmonic frequencies and anharmonic constants for the So state are determined. A hitherto unknown Darling-Dennison resonance of the overtones of v, with the 52 state is found. 1

Sub-Doppler UV spectroscopy by resonance-enhanced two-photon ionization: the structure of the benzene20,22Ne cluster

In this work it is demonstrated that mass selected multiphoton ionization is a powerful technique for high resolution spectroscopy, isotope cluster separation and investigation of the structure of van der Waals clusters. The rotationally resolved UV spectra of the benzene-20Ne and benzene-22Ne clusters are selectively measured in a natural isotopic mixture of benzene and benzene-Ne clusters in a cooled supersonic jet. The analysis of these spectra yields accurate values for the rotational constants of both species. From this data it is found that the Ne atom is located on the C6 rotational axis of the benzene ring at an average distance of 3.46 Å with a slight difference for the two isotopes. This distance decreases by 40 mÅ when benzene is electronically excited. The influence of the large amplitude van der Waals vibrations on the average bond length is discussed

Non-sequential triple ionization in strong fields

We consider the final stage of triple ionization of atoms in a strong linearly polarized laser field. We propose that for intensities below the saturation value for triple ionization the process is dominated by the simultaneous escape of three electrons from a highly excited intermediate complex. We identify within a classical model two pathways to triple ionization, one with a triangular configuration of electrons and one with a more linear one. Both are saddles in phase space. A stability analysis indicates that the triangular configuration has the larger cross sections and should be the dominant one. Trajectory simulations within the dominant symmetry subspace reproduce the experimentally observed distribution of ion momenta parallel to the polarization axis.Comment: 9 pages, 8 figures, accepted for publication in Phys. Rev.

Pathways to double ionization of atoms in strong fields

We discuss the final stages of double ionization of atoms in a strong linearly polarized laser field within a classical model. We propose that all trajectories leading to non-sequential double ionization pass close to a saddle in phase space which we identify and characterize. The saddle lies in a two degree of freedom subspace of symmetrically escaping electrons. The distribution of longitudinal momenta of ions as calculated within the subspace shows the double hump structure observed in experiments. Including a symmetric bending mode of the electrons allows us to reproduce the transverse ion momenta. We discuss also a path to sequential ionization and show that it does not lead to the observed momentum distributions.Comment: 10 pages, 10 figures; fig.6 and 7 exchanged in the final version accepted for publication in Phys. Rev.

Selective bond-breaking in formic acid by dissociative electron attachment.

We report the results of a joint experimental and theoretical study of dissociative electron attachment to formic acid (HCOOH) in the 6-9 eV region, where H- fragment ions are a dominant product. Breaking of the C-H and O-H bonds is distinguished experimentally by deuteration of either site. We show that in this region H- ions can be produced by formation of two or possibly three Feshbach resonance (doubly-excited anion) states, one of which leads to either C-H or O-H bond scission, while the other can only produce formyloxyl radicals by O-H bond scission. Comparison of experimental and theoretical angular distributions of the anion fragment allows the elucidation of state specific pathways to dissociation

High-resolution UV spectrum of the benzene—N2 van der Waals complex

The rotationally resolved spectrum of the 610 band of the S1 ← S0 electronic transition of the benzene—N2 van der Waals complex has been recorded and 119 transitions assigned. The C6H6·N2 complex, produced in a pulsed molecular beam, was detected by mass-selected two-photon two-colour ionization employing a high-resolution (ΔνUV = 100 MHz, fwhm) pulsed-amplified cw laser for the resonant intermediate excitation. The observed rotational structure is that of a rigid symmetric top with weaker additional rotational transitions most likely arising from the free internal rotation of the N2 in the plane parallel to the benzene ring. The N2 is located parallel to the benzene ring at a distance of 3.50 Å; this decreases by 45 mÅ in the excited electronic state

Van der Waals bond lengths and electronic spectral shifts of the benzene---Kr and benzene---Xe complexes

Rotationally resolved UV-spectra are presented for the 610 bands of benzene---Kr and benzene---Xe complexes yielding precise rotational constants and van der Waals bond lengths for the ground and excited vibronic state, and electronic band shifts. These value complement the previously published data for the other rare gases and the various quantities have now been determined for all the benzene—rare gas complexes. Measured values of the bond length were used to calculate the band shifts from recent theoretical predictions. They are compared with the experimental values of this work

Rotationally resolved ultraviolet spectra of benzene-noble gas van der Waals clusters

Sub-Doppler electronic spectra with hundreds of resolved rotational lines are now available for benzene-Ar dimers and trimers. From their analysis the structure of these clusters is precisely determined. The analysis of two bands, 6 0 1 and 16 0 2 , of C6H6 · Ar is presented in detail. It leads to accurate values of the van der Waals bond length in the electronic ground and excited state. The change in frequency upon clustering is found to be a factor of 17 larger for the overtone of the out-of-plane modev 16 than for the in-plane vibrationv 1. This can be tentatively explained by an interaction of the low frequency out-of-plane motion of the ring with the van-der-Waals motion of the Ar atom