Abstract
Experiments involving molecules which are truly isolated for time periods .exceeding several milliseconds require special techniques for particle storage at low pressure. In the case of charged species, crossed electric and magnetic fields can be used to restrain particle motion for time periods exceeding several hours, establishing conditions in the laboratory which exist in nature only in the interstellar medium. The phenomenon of ion cyclotron resonance provides a sensitive and selective means to detect charged particles stored in a magnetic field. At pressure below 10 torr stored ions are forced to maintain equilibrium with their environment by the absorption and emission of infrared radiation rather than in collisions with other molecules. Infrared lasers offer the possibility of upsetting this equilibrium by exposing molecules to an enormous photon flux at specific wavelengths. What fraction of the ion population will absorb infrared radiation at a specific wavelength? Can more than one photon be absorbed?
Contribution No. 6516
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Excitation of neutral CH3OH does not contribute to the observed laser-induced chemistry because of the brief residence time of neutrals in the ion storage and irradiation region. This is discussed in detail elsewhere. Since both CH3OH and (CH3OH) 2H+ absorb in the 10-µm region, it might be expected that (CH3OH) H+ (OH2) also absorbs. However, no evidence is obtained for laser excitation enhancing the reverse of reaction 3 or for multiphoton dissociation of (CH3OH) H+ (OH2) to CH3OH2 + and H2O (25 kcal/ mol) . Both results suggest that (CH3OH) H (OH2) , in comparison with (CH3OH) 2H , is not heated significantly by the infrared laser. Based on the proposed kinetic scheme, heating might result in a slight decrease in k1, for reaction 1, which would be difficult to detect.
At the laser powers used, the typical rate for absorbing a single photon (103 s-1 for a transition with absorption cross section of 10-17 cm2) is very much slower than the decomposition rate (>107 s-1) of the intermediate. Thus the enhanced reaction rate is due to excitation of reactants, not to the intermediate.
C.A. Wight, J.L. Beauchamp, J. Am. Chem. Soc., submitted for publication.
C.A. Wight, J.L. Beauchamp, manuscript in preparation.
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Thorne, L.R., Wright, C.A., Beauchamp, J.L. (1982). Infrared Photochemistry of Gas Phase Ions. In: Ion Cyclotron Resonance Spectrometry II. Lecture Notes in Chemistry, vol 31. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-50207-1_3
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