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  • 1
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Doubly charged ion mass spectra have been obtained for 42 chlorinated and brominated n-alkane (methyl through octyl) hydrocarbons. A double focusing Hitachi RMU-7L mass spectrometer, operated at 1.6kV accelerating voltage, has been used to measure the spectra. Molecular doubly charged ions have not been observed. Intense fragment ions have been produced from extensive H and halogen loss as well as C—C bond rupture of the parent molecule. The most abundant ions in the doubly charged ion spectra observed in this investigation resulted from reactions of [Cl]2+·, [Br]2+·, [CCL2]2+, [C2H2Cl]2+·, [C3H2]2+, [C3HCl]2+, [C3HBr]2+, [C4H3]2+·, [C4H4]2+, [C4H6Br]2+·, [C4H8Br]2+·, [C5H2]2+, [C6H6]2+, [C6H8]2+ and [C7H8]2+. The prominent doubly charged fragment ions formed by electron impact of the smaller halogenated alkanes generally contained halogen, whereas ions of the type [CnHx]2+ were dominant in the spectra of higher molecular weight mono- and dihalogenated alkanes. Appearance energies of several ions have been measured. A geometry optimized quantum mechanical SCF treatment has been used to compute energies, charge densities and structures of doubly charged halogenated alkane ions.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 15 (1980), S. 312-316 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The doubly charged ion mass spectra for 12 aliphatic nitriles (1-9 carbon atoms) have been obtained using an Hitachi RMU-7L double focusing mass spectrometer. These spectra show some characteristic features such as extensive loss of hydrogen and the grouping of ions in the spectra into n-1 groups where n is the number of carbon atoms in the molecule (n〈6). There are no indications of HCN or CN loss in the doubly charged ion spectra of the monosubstituted nitriles. SCF calculations of the energy and structure of doubly charged ions in the propionitrile spectra have been carried out.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 19 (1984), S. 412-422 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Doubly charged ion mass spectra of 23 alkenes have been measured using a double focusing Hitachi RMU-7L mass spectrometer. Ion mass spectra were obtained using 100 eV electron energy and 3.2 kV ion accelerating voltage. Each 2E spectrum was determined using the olefinic compound under investigation as the target gas. In general, spectra are dominated by fragment ions which result from extensive hydrogen loss from the doubly charged molecular ion. Appearnce energies have been measured for intense fragment ions in each spectrum.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 21 (1986), S. 69-75 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The energetics, structures, stabilities and reactivities of[CnH2]2+ ions have been investigated using computational methods and experimental mass spectrometric techniques. Spontaneous decompositions of [CnH2]2+ into [CnH]+ + H+ products, observed for ions with odd-n values, have been explained by invoking the formation of excited triplet states. Even-n [CnH]+ ions possess triplet ground states with low-lying excited states, whereas odd-n ions have triplet states with energies several eV above ground singlet states. Radiationless transitions of vibrationally excited long-lived triplet state ions into singlet state continua are suggested as possible mechanisms for spontaneous deprotonation processes of odd-n [CnH2]2+ ions. Evidence for these long-lived excited states has been obtained in bimolecular single electron transfer reactions.
    Additional Material: 7 Ill.
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  • 6
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Potential energy curves have been computed for [C2H6]2+ ions and the results used to interpret the conspicuous absence of these ions in 2E mass spectra and in charge-stripping experiments. The energies and structures of geometry-optimized ground-state singlet and excited-state triplet [C2H6]2+ ions have been determined along with energies for different decomposition barriers and dissociation asymptotes. Although singlet and triplet [C2H6]2+ ions can exist as stable entities, they possess low energy barriers to decomposition. Vertical Franck-Condon transitions, involving electron impact ionization of ethane as well as charge-stripping collisions of [C2H6]+ ions, produce [C2H6]2+ ions which promptly dissociate since they are formed with energies in excess of various decomposition barriers. Appearance energies computed for doubly-charged ethane fragment ions are in accordance with experimental values.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cross sections for charge transfer reactions of organic ions containing oxygen have been obtained using time-of-flight techniques. Charge transfer cross sections have been determined for reactions of 2.0 to 3.4 keV ions produced by electron impact ionization of oxygen containing molecules such as methanol, ethanal and ethanol. Experimental cross section magnitudes have been correlated with reaction energy defects computed from ion recombination energies and target ionization energies. Large cross sections are observed for reacting systems with small energy defects.
    Additional Material: 6 Ill.
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  • 8
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Doubly charged ion mass spectra of alkyl-substituted furans and pyrroles were obtained using a double-focusing magnetic mass spectrometer operated at 3.2 kV accelerating voltage. Molecular ions were the dominant species found in doubly charged spectra of lower molecular weight heterocydic compounds, whereas the spectra of the higher weight homologues were typified by abundant fragment ions from extensive decomposition. Measured doubly charged ionization and appearance energies ranged from 22.8 to 47.9 eV. Ionization energies were correlated with values calculated using self-consistent field-molecular orbital techniques. A multichannel diabatic curve-crossing model was developed to investigate the fundamental organic ion reactions responsible for development of doubly charged ion mass spectra. Probabilities for Landau-Zener type transitions between reactant and product curves were determined and used in the collision model to predict charge-transfer cross-sections, which compared favorably with experimental cross-sections obtained using time-of-flight techniques.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of the collision gas on doubly charged ion mass spectra of a selected number of hydrocarbons has been examined. Relative abundances of various product ions in 2E spectra, resulting from charge exchange collisions of doubly charged hydrocarbon ions, do not vary drastically as the collision gas is varied. However, the absolute intensities of these doubly charged ion mass spectra increase significantly when the collision gas is changed from argon to methane to isobutane. Tbese observations are rationalized in terms of a multichannel diabatic curve crossing model.
    Additional Material: 11 Ill.
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  • 10
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Positive and negative cluster ions in methanol have been examined using a direct fast atom bombardment (FAB) probe technique. Positive ion (CH3OH)IIH + clusters with n = 1-28 have been observed and their clusters are the dominant ions in the low-mass region. Cluster-ion reaction products (CH3OH)II(H2O)H+ and (CH3OH)II(CH3OCH3)H+ are observed for a wide range of n and the abundances of these ions decrease with increasing n. The negative ion (CH3OH)II(CH3O)- clusters are also readily observed with n = 0-24 and these form the most-abundant negative ion series at low n. The (CH3OH)II(CH2O)-, (CH3OH)II(HIIO)(CH2O)- and (CH3OH)II(H2OXCH3O)- cluster ions are formed and the abundances of these ions approach those of the (CH3OH)II(CH3O)- ion series at high n. Cluster-ion structures and energetics have been examined using semi-empirical molecular orbital methods.
    Additional Material: 9 Ill.
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