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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 107 (1997), S. 9842-9851 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The ratio of the nascent population of C2 (X 1Σg+) to C2 (A 1Πu) to C2 (B′ 1Σg+) produced from the photodissociation of C2H at 193 nm has been measured using laser induced fluorescence. This technique is typically used to measure rotational and vibrational distributions in a given electronic state. Here, we have extended the technique to measure the relative electronic distributions in the C2 photofragment. From the simultaneous measurement of the Mulliken (X 1Σg+–D 1Σu+) and Freymark (A 1Πu–E 1Σg+) systems, the nascent population ratio of C2 (A 1Πu) to C2 (X 1Σg+) molecules was determined. Similarly, from the measurement of the Deslandres–D'Azumbuja (A 1Πu–C 1Πg) and the LeBlanc (B′ 1Σg+–D 1Σu+) systems, the nascent population ratio of C2 (A 1Πu) to C2 (B′ 1Σg+) was determined. The overall ratio for the production of C2 in the X:A:B′ electronic states was found to be 1:19:1.4. These results along with the results of high quality ab initio calculations of Cui and Morokuma (unpublished) are used to discuss the photodissociation dynamics of C2H at 193 nm. Furthermore, these results should aid in the analysis and modeling of cometary spectra of C2 . © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 115 (2001), S. 6012-6017 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photodissociation dynamics of the dibromomethane cation, CH2Br2+, have been studied by means of ion velocity imaging and time-of-flight mass spectroscopy methods at 355 nm. The dibromomethane cation is produced through the direct ionization of the neutral molecule with a pulsed 118 nm laser. The translational energy distribution shows that the CH2Br+ fragment is formed in highly vibrationally excited states with two distinguished dissociation channels following a parallel excitation from 2b2 to 3b2 of the parent ion. The broad fast speed distribution is fit with two Gaussian functions, from which a branching ratio of Br*(2P1/2) to Br(2P3/2) is determined as 2.2:1. The sharp peak with very slow speed was modeled with a Boltzmann distribution with a temperature of 300 K. This channel contributes ∼4.5% to the reaction and is proposed to proceed on the ground state surface following internal conversion. Ab initio calculations for both the parent and the fragment ions have been performed that strongly support the proposed dissociation mechanisms. © 2001 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 117 (2002), S. 2578-2585 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photochemistry of bromoform is of considerable importance to understanding the impact of short-lived halogen species on bromine chemistry in the atmosphere. In the present work, the products of the ultraviolet photodissociation of bromoform at 234 and 267 nm are determined by time-of-flight mass spectrometry and velocity ion imaging. Both ground Br (2P3/2) and spin–orbit excited Br (2P1/2) atoms are found to be formed via resonance-enhanced multiphoton ionization detection. Radical products are detected via vacuum ultraviolet photoionization at 118 nm. The results indicate that there is a primary molecule bromine elimination channel consisting of CHBr+Br2. The quantum yields for atomic Br and molecular Br2 elimination channels are determined from the time-of-flight spectra to be 0.74 and 0.26 at 234 nm, respectively. At 267 nm, they are 0.84 and 0.16, respectively. Energy and angular distributions are deduced from the 2D images of Br, CHBr, and CHBr2. The direct studies described in this paper on the photodissociation of bromoform suggest that the current atmospheric photochemical models that do not anticipate the formation of Br2 need to be reinvestigated to determine their implications for atmospheric bromine chemistry. © 2002 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 113 (2000), S. 3651-3657 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Photodissociation of acetone cations, CH3COCH3+, at 355 nm has been studied by means of the ion velocity imaging technique. Acetone cations are produced via direct photoionization of a supersonic beam of acetone at 118 nm generated by frequency tripling the 355 nm laser. Only the acetyl cation, CH3CO+, could be detected as a dissociation product in the time-of-flight mass spectrometer. The acetyl ion signal depends upon the fifth power of the 355 nm laser energy, while the acetone ion signal depends upon the third power. This suggests that the fragment ion is produced via two-photon absorption of 355 nm photons by the acetone cation. The total translational energy distribution and angular distribution of acetyl cation were derived from the 2D images of CH3CO+ for the reaction CH3COCH3++2hν355 nm→CH3CO++CH3*. The translational energy distribution suggests that methyl radicals are produced in two electronically excited states, the Rydberg 3s 1 2A1′ and the valence 1 2A″ states. The anisotropy parameter β shows that the Rydberg state is formed via a perpendicular excitation and the valence state via a parallel transition. © 2000 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1573-0794
    Keywords: Carbon disulfide ; cometary atmosphere ; ion imaging ; photochemical reaction ; sulfur branching ratio
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract New experimental methods for studying photochemical reactions aregiven and the strength and weakness are briefly discussed. References and bibliographies for these photochemical studies are presented. A case study of carbon disulfide (CS2) that uses vacuum ultraviolet lasers, time-of-flight mass spectrometry, molecular beams and ion velocity imaging to measure andcharacterize the products is described. These results are compared with previous studies and the difficulties involved in understanding these results are pointed out.
    Type of Medium: Electronic Resource
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