Generation and orientation of organoxenon molecule H-Xe-CCH in the gas phase

Journal Article · Fri Mar 14 04:00:00 EDT 2008 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2837656· OSTI ID:21104002

Poterya, Viktoriya; Votava, Ondrej; Farnik, Michal ^[1]; Oncak, Milan; Slavicek, Petr ^[2]; Buck, Udo ^[3]; Friedrich, Bretislav ^[4]

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1. J. Heyrovsky Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Prague 8 (Czech Republic)
2. Department of Physical Chemistry, Institute of Chemical Technology, Technicka 5, Prague 6 (Czech Republic)
3. Max-Planck Institut fuer Dynamik und Selbstorganization, Bunsenstrasse 10, D-37073 Goettingen (Germany)
4. Fritz-Haber-Institut der Max-Planck Gesellschaft, Faradayweg 4-6, D-14195 Berlin (Germany)

We report on the first observation of the organoxenon HXeCCH molecule in the gas phase. This molecule has been prepared in a molecular beam experiment by 193 nm photolysis of an acetylene molecule on Xe{sub n} clusters (n{approx_equal}390). Subsequently the molecule has been oriented via the pseudo-first-order Stark effect in a strong electric field of the polarized laser light combined with the weak electrostatic field in the extraction region of a time-of-flight spectrometer. The experimental evidence for the oriented molecule has been provided by measurements of its photodissociation. For comparison, photolysis of C{sub 2}H{sub 2} on Ar{sub n} clusters (n{approx_equal}280) has been measured. Here the analogous rare gas molecule HArCCH could not be generated. The interpretation of our experimental findings has been supported by ab initio calculations. In addition, the experiment together with the calculations reveals information on the photochemistry of the HXeCCH molecule. The 193 nm radiation excites the molecule predominantly into the 2 {sup 1}{sigma}{sup +} state, which cannot dissociate the Xe-H bond directly, but the system evolves along the Xe-C coordinate to a conical intersection of a slightly nonlinear configuration with the dissociative 1 {sup 1}{pi} state, which then dissociates the Xe-H bond.

• OSTI ID: 21104002
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 10 Vol. 128; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
ACETYLENE
COMPARATIVE EVALUATIONS
DISSOCIATION
MOLECULAR BEAMS
MOLECULAR CLUSTERS
PHOTOCHEMISTRY
PHOTOLYSIS
STARK EFFECT
TIME-OF-FLIGHT SPECTROMETERS
XENON COMPOUNDS