1. Diagnosis of a benzene discharge with a mass-selective spectroscopic technique Felix Güthe, Hongbin Ding, Thomas Pino and John P. Maier Institute of Physical Chemistry, University of Basel, Klingelbergstrasse 80, CH-4056 Basel, Switzerland. Mass spectrometry with different laser excitation schemes Diagnosis of a plasma with REMPI detection Identification of molecules by R2PI spectroscopy in the UV range References A new experiment has been built in the group to perform resonance enhanced multi photon ionization (REMPI) studies of the neutral C n H m clusters. They are produced in a plasma formed by a pulsed discharge source 1,2 and are quenched by cooling in a supersonic expansion. The apparatus couples the discharge source with a REMPI detection in a linear time of flight (TOF) mass-analyzer (R 50% = ~900 ), enabling to combine the information on the masses and the electronic spectra. 200 or more species can be recorded simultaneously. After deflection of charged species the neutral molecules are ionized by lasers. For the ionization either one two photons of the same wavelength (R2PI) or two photons of different wavelength (R2C2PI) can be used. 1) F. Güthe; H. Ding; T. Pino; J. P. Maier, Chemical Physics, accepted. 2) T. Pino; H. Ding; F. Güthe; J. P. Maier, Journal of Chemical Physics, 2208, 114, (2001). 3) http://www.chemie.unibas.ch/~linnartz/ 4) W. Jenneskens, M. Sarobe, Polycyclic Aromatic Compounds,. 14/15, 169 (1999). 5) C. Lifshitz, G. Reuben, J. Chem. Phys. 50, 951 (1969). Acknowledgment Mass spectra of the neutral clusters produced with an benzene discharge recorded with different ionization wavelengths: A VUV-laser in one case (F 2 -excimer at 157 nm; 7.59 eV) and a spectrum taken during a scan from 278-290 nm (~4.5 eV). The arrows point to the masses 128 and 178, which are coinciding with the masses of the first members of the polycyclic aromatic hydrocarbons (PAH). But only the electronic spectra can reveal the identity of the carriers of this mass peaks ! The authors would like to thanks Georg Holderied and Dieter Wild and the mechanical workshop for their technical assistance. Tomasz Motylewski and Danielle Furio (LPPM, Orsay France) are also kindly thanked for their help in developing the software of the experiment. For the benzene discharge we recorded R2PI spectra between 320 and 280 nm. Electronic spectra of more 30 different molecules have been obtained. In the graphs the spectra of phenylacetylene (C 8 H 6 ), styrene (C 8 H 8 ), indene (C 9 H 8 ), methylstyrene (C 9 H 10 ), fluorene (C 13 H 10 ), tolane (C 14 H 10 ) as well as the of molecule C 10 H 8 are shown. From these 6 molecules could be identified by there spectra from literature. Note that the spectrum of. C 14 H 10 is not that of anthracene or the phenanthrene, the compact all 6-ring PAHs, but that of the tolane molecule. The strong S 0 -S 2 phenantrene transition is clearly absent. The spectrum of the C 10 H 8 molecule is not that of the bicyclic naphthalene, but probably that of a monocycclic substituted benzene. U 0 =500-1000V Width=10-200  s I=0.2-5 A Picture of the plasma from a slit nozzle discharge on C 2 H 2 taken from H. Linnartz 3. In this work a nozzle of circular geometry with benzene as precursor gas was used but could not be photographed. The species identified in this work are known as intermediates in several chemical models for combustion. The ethynyl-PAHs (E-PAH) and cyclopentafused PAH (CP-PAH) have been proposed to be intermediates in fullerene formation and in the build up of larger carbon species. Thus the direct sampling of the benzene discharge in the molecular beam reflects the pyrolysis process in an early stage, where the most stable isomers have not yet been formed. Their formation might occur at later stage at higher temperature 4. The formation of the neutral species seen in the spectra can be assumed to occur by two stages in analogy to cation chemistry known from electron impact work in high pressure sources 5 : Combination of a plasma discharge source with spectroscopic characterisation by REMPI. -A model system for hydrocarbon flames?? Chemistry in the discharge plasma: Conclusion -Identification of other species (C 6 D 6 as precursor...) to gain deeper understanding of the chemistry in plasmas -Characterisation of other mixtures -Work in the visible. Future work The produced C n H m species are important intermediates in combustion processes and interstellar chemistry. Their electronic spectra are important for their identification and could be related to the diffuse interstellar band problem.