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F Stienkemeier

Publications and source records attributed to F Stienkemeier.

8 recordsLinked to original sources

Spectroscopy of Cs attached to helium nanodroplets.

Cesium oligomers are formed on helium nanodroplets which are doped with one or a few Cs atoms. The monomer absorption of the first electronic p<--s transition upon laser excitation is probed. Spectra employing laser-induced fluorescence, beam depletion, and resonant photoionization are compared. In particular, mass-resolved photoionization allows us to specifically probe excitation induced processes such as, e.g., the formation of cesium-helium exciplexes. Absorption spectra of Cs dimers and trimers are recorded in the spectral region accessible by a Ti:sapphire laser. Assignment of dimer spectra is achieved by comparison with model calculations based on ab initio potentials. Electronic absorption lines of Cs trimers are attributed to transitions in the quartet manifold.

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Formation times of RbHe exciplexes on the surface of superfluid versus normal fluid helium nanodroplets.

Nanodroplets of either superfluid 4He or normal fluid 3He are doped with Rb atoms that are bound to the surface of the droplets. The formation of RbHe exciplexes upon 5P(3/2) excitation is monitored in real time by femtosecond pump-probe techniques. We find formation times of 8.5 and 11.6 ps for Rb 4He and Rb 3He, respectively. A comparison to calculations based on a tunneling model introduced for these systems by Reho et al. [J. Chem. Phys. 113, 9694 (2000)]] shows that the proposed mechanism cannot account for our findings. Apparently, a different relaxation dynamics of the superfluid opposed to the normal fluid surface is responsible for the observed formation times.

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Laser-induced fluorescence spectroscopy of 3,4,9,10-perylenetetracarboxylic-dianhydrid in helium nanodroplets.

Electronic spectra of the S1<--S0 transition of the 3,4,9,10-perylenetetracarboxylic-dianhydrid (PTCDA) monomer isolated in superfluid helium nanodroplets have been measured by means of laser-induced fluorescence. The 0(0)(0) transition appears at 20,988 cm(-1) as the dominant line. We obtain clearly resolved the vibrational structure of the molecule. A comparison to Raman spectra of PTCDA films on metallic substrates and PTCDA crystals as well as with calculated frequencies provides the identification of the different modes. The enhanced resolution in the low temperature helium environment and the obtained line positions provide new information about structural properties of perylene derivatives.

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Formation and stability of high-spin alkali clusters.

Helium nanodroplet isolation has been applied to agglomerate alkali clusters at temperatures of 380 mK. The very weak binding to the surface of the droplets allows a selection of only weakly bound, high-spin states. Here we show that larger clusters of alkali atoms in high-spin states can be formed. The lack of strong bonds from pairing electrons makes these systems nonmetallic, van der Waals-like complexes of metal atoms. We find that sodium and potassium readily form such clusters containing up to 25 atoms. In contrast, this process is suppressed for rubidium and cesium. Apparently, for these heavy alkalis, larger high-spin aggregates are not stable and depolarize spontaneously upon cluster formation.

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Formation of K*He exciplexes on the surface of helium nanodroplets studied in real time.

Superfluid helium nanodroplets are doped with potassium atoms to form complexes with the alkali atom residing on the surface of the droplets. Dispersed laser-induced fluorescence spectra of such systems already revealed the formation of M(*)He ( M = Na,K) exciplexes upon electronic excitation [Reho et al., Faraday Discuss. 108, 161 (1997)]. By means of femtosecond pump-probe spectroscopy, this formation process now is followed in real time. We find K(*)He(n = 1) to be formed within 180 fs. Furthermore, the existence of exciplexes with n>1 is quantified suggesting that the first ring around the potassium atom contains four helium atoms.

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Photoinduced Chemical Dynamics of High-Spin Alkali Trimers

Nanometer-sized helium droplets, each containing about 10(4) helium atoms, were used as an inert substrate on which to form previously unobserved, spin-3/2 (quartet state) alkali trimers. Dispersed fluorescence measurements reveal that, upon electronic excitation, the quartet trimers undergo intersystem crossing to the doublet manifold, followed by dissociation of the doublet trimer into an atom and a covalently bound singlet dimer. As shown by this work, aggregates of spin-polarized alkali metals represent ideal species for the optical study of fundamental chemical dynamics processes including nonadiabatic spin conversion, change of bonding nature, and unimolecular dissociation.

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