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  • 1
    Electronic Resource
    Electronic Resource
    Decomposition of highly vibrationally excited CDCl3 (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 5191-5197 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Decomposition of highly vibrationally excited CDCl3 was studied in the time domain by measuring laser-induced fluorescence from one of the decomposition products CCl2 or by observing luminescence from CCl2 radical fragments produced in the A˜(1B1) state following IR excitation. It is shown that highly vibrationally excited CDCl3 can be made via two different routes: i(Slashthrough accent mark)mple optical absorption of an incident 13CO2 laser pulse or through collision-moderated energy pooling coupled with photon absorption. Higher fluence measurements are consistent with the former and support previous claims that the infrared multiphoton decomposition probability for CDCl3 is pressure independent. At a lower fluence the vibrational up-pumping mechanism apparently relies heavily upon collisions, which supports other claims that the decomposition probability is pressure dependent. The results of the present work reconcile these previous disparate claims. Furthermore, there is an indication that the vibrational energy transferred during a collision could be much larger than collision-induced dipole selection rules would allow. In some of the experiments, electronically excited CCl2 fragments are created but only through post-laser-pulse collisions that appear to involve exchanges of very large amounts of vibrational energy. By contrast, no electronically excited CCl2 is produced following excitation with the CO2 laser alone. The experiments also corroborate an earlier prediction that the extent of reaction is governed by adiabatic expansion of the centrally heated zone, even at pressures as low as 0.66 kPa, rather than by diffusion, as is commonly believed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.462759
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  • 2
    Electronic Resource
    Electronic Resource
    Detection of O(1D) produced in the photodissociation of O2. I. Identification of the 3Σu− and 3Πu Rydberg states in 113–130 nm (2000)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 112 (2000), S. 1763-1768 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The metastable O(1D) atom produced in the photodissociation of O2 in the wavelength region 113–130 nm was detected by measuring the 762 nm fluorescence of the transition O2(b 1Σg+→X 3Σg−). The excited states of O2 were classified as either the 3Σu− state that produces O(1D)+O(3P), or the 3Πu state that produces O(3P)+O(3P). Our quantum yield measurements of O(1D) found bands of both pure and overlapped 3Σu− and 3Πu states. Five bands were found to produce O(1D), including the longest, second, and third bands and two additional bands near 115.3 and 113.8 nm that were assigned as the E 3Σu−(v′=3–4) states. Three bands were assigned to the F 3Πu(v′=0–2) state. We also found a state at 116.2 nm, which did not produce O(1D), but produced weak visible fluorescence. The possibility of attributing the fluorescence to a transition D 3Σu+–C 3Πg was discussed. © 2000 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.480739
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  • 3
    Electronic Resource
    Electronic Resource
    Detection of O(1D) produced in the photodissociation of O2. II. Identification of the 3Σu− and 3Πu Rydberg states in 105–113 nm (2001)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 114 (2001), S. 792-797 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The production of O(1D) from O2 by photodissociation was measured in the 105–113 nm wavelength region. The quantum yields of O(1D) were employed to identify the excited states as 3Σu− or 3Πu, where the former correlated with the production of O(1D) and the latter production of O(3P) only. Many bands of E, E′ of 3Σu− and F, F′ 3Πu, were found with their vibrational states identified. Several bands had mixed states, such as the (0,0) and (1,0) bands of D′ 3Σu−←X 3Σg− transition which had smaller than unity quantum yields of O(1D) due to the perturbation caused by the nearby states D′ 3Σu+(v′=1,2) at 112.0 and 110.0 nm. The bands of npσu 3Πu state in the region of 105–110 nm are in agreement with the assignments of other works, and a band near 107.3 nm is consistent with the predicted band position of the F 3Πu(v′=6) upper-state. © 2001 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.1330231
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