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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 1452-1459 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ultraviolet photoelectron spectra have been measured for argon clusters prepared in pulsed supersonic expansions of both pure and seeded mixtures of argon. The broad band spectra show structural features which relate to the degree of condensation and hence the mean cluster size obtained at different stagnation pressures. These are interpreted in terms of an ion–core hypothesis with diatomics-in-molecules calculations being used to simulate spectral features. The analysis shows that Ar+3 cores are formed in the initial ionization process of very small clusters, with the Ar+13 core becoming dominant for all larger clusters and for the condensed state of argon.
    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 95 (1991), S. 1473-1478 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Ultraviolet photoelectron spectra have been measured for pulsed supersonic beams of krypton and xenon as dilute mixtures in helium. The spectra exhibit broad bands which are located at lower ionization energies relative to the monomer ion states, 2P3/2 and 2P1/2, with which they correlate. The structural features of the spectra, particularly in the first band group, become more complex with increasing condensation, apparently relating to the mean cluster size associated with each spectrum. The spectra are interpreted using the cluster-size dependent core-ion model developed to explain the analogous spectra of the argon clusters. The argon clusters spectra were interpreted as showing the presence of Ar+3, Ar+7, and Ar+13 core ions, with Ar+3 involved in the ionization of small neutral clusters, and Ar+13 produced by the dominant ionization mechanism in large clusters as well as in solid argon. The krypton and xenon clusters show variations of this behavior. The relatively large spin-orbit splitting of the Kr+ and Xe+ p-hole states is reflected in the two band groups observed in the respective Kr and Xe clusters spectra. The lower ionization energy band group in each case exhibits structural features similar to those observed for the argon clusters spectra. The krypton spectra indicate, that for the largest clusters, all three core-ion mechanisms are operative; whereas, for xenon, the largest clusters show only the triatomic core ion, Xe+3, as involved in the ionization mechanism. The high pressure clusters spectra of argon, krypton, and xenon are effectively identical with those reported for their respective condensed thin films, indicating that these variations in the core-ion mechanism of ionization are also responsible for the differences observed in the ultraviolet photoemission spectra of the rare-gas solids.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of the American Chemical Society 105 (1983), S. 6788-6790 
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of the American Chemical Society 110 (1988), S. 3458-3461 
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 642-650 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The He i photoelectron spectra of gas-phase nitrogen dimer and nitrogen clusters have been measured in a pulsed cluster beam. The dimer (N2)2 is characterized by broad bands with vertical ionization energies which are 0.3±0.1 eV lower than for N2 monomer. The bands observed for a mixture of small clusters, estimated to be of average size N¯=10, are identical to the dimer bands except for further shifts of 0.3 eV to lower ionization energies. The clusters bandwidths and band shapes are virtually the same as measured for thin films of condensed N2, indicating that the nitrogen dimer (N2)2 is the ionization chromophore in each case. This offers support for Haberland's hypothesis that ionization of any Mn cluster produces the ion M+2Mn−2 provided M is a closed-shell atom or molecule. The theory of electronic relaxation polarization of the dielectric medium, which explains the gas-to-solid ionization energy shifts, is modified for the case of finite clusters and to account for dimer ion formation.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 85 (1986), S. 6261-6266 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The He i photoelectron spectrum of (NH3)2 is shown to have only a single broad unstructured ionization band near 10 eV. This demonstrates the equivalence or near-equivalence of the nitrogen lone-pair orbitals of each NH3 unit in the dimer structure. While theory has generally predicted that (NH3)2 has a classical structure with a near-linear N--H–N linkage, such a structure would be expected to show two ionization bands separated by about 1.5 eV. However analysis of the observed low ionization energy band suggests that a maximum possible band separation would be only 0.5 eV for ionization from the nitrogen lone-pair orbitals. While this result concurs with the nonclassical structure for (NH3)2 proposed by Klemperer and co-workers, it does not exclude the symmetric C2h structure as a likely equilibrium geometry for the dimer. On the contrary, it is argued that the photoelectron spectrum is supportive of the latter structure. Split-valence basis Hartree–Fock calculations on (NH3)2 at various nonclassical geometries indicate that the dimer could have the symmetric C2h geometry but that a relatively shallow potential energy surface for asymmetric van der Waals vibrations would be responsible for the nonzero dipole moment observed by rotational spectroscopy. This conclusion corroborates the finding of the most recent ab initio calculations on (NH3)2 by Latajka and Scheiner.
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 85 (1986), S. 4304-4310 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The He i photoelectron spectrum of the gas-phase complex formed by dimethyl ether and sulfur dioxide has been measured using a pulsed free jet expansion of a mixture of the two gases. A spectrum stripping procedure was used to remove the respective monomer bands from the measured spectrum giving a spectrum assigned to the 1:1 complex (CH3)2O⋅SO2. Interpretation of the spectrum with the aid of ab initio molecular orbital calculations shows that ionization bands associated with (CH3)2O are increased in energy by up to 0.4 eV, whereas those associated with SO2 are decreased in energy by up to 0.9 eV. Ab initio calculations on the dimethyl ether–sulfur dioxide complex, performed at the 3-21G* level, predict an intermolecular O--S separation of 2.355 A(ring) with this direction being displaced 30° from the symmetry axis of the (CH3)2O but approximately perpendicular to the SO2 molecular plane. The monomer dipoles are oriented approximately antiparallel in the complex.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 84 (1986), S. 6526-6527 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: He i photoelectron spectra are presented for the NO dimer, (NO)2, and for a mixture of higher clusters, (NO)nn≥3. The NO dimer shows a weak second band associated with a shake-up transition at a vertical I.E. of 10.8 eV, 1.9 eV above that of the first band. This disagrees with a theoretical estimate of 2.7 eV. The ratio of intensities of these two bands is measured as 1:0.18 in comparison with the theoretical estimate of 1:0.28. The spectrum of the mixture of higher clusters shows the analogous two bands at vertical I.E.s of 8.4 and 10.8 eV, respectively. The band separation of 2.4 eV is close to the value of 2.6 eV observed in the photoemission spectrum of condensed NO.
    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 He I photoelectron spectra of gas-phase oxygen dimer and oxygen clusters have been measured in a pulsed beam. The spectrum of the dimer (O2)2 is characterized by broad bands which show 1:1 correspondence with those of the monomer O2. The vertical ionization energies are 0.2 ± 0.1 eV lower than those of the monomer. The photoelectron bands observed for mixtures of small clusters are identical to the dimer bands except for further shifts of up to ∼0.3 eV to lower ionization energies. The clusters spectra show bandwidths and bandshapes which are effectively the same as those measured for thin films of condensed O2, indicating that the oxygen dimer (O2)2 is the ionization chromophore in each case. This supports the dimer-ion hypothesis proposed for the ionization of van der Waals clusters of closed-shell molecules. Ab initio calculations on (O2)2+ show good agreement with the experimental data, and suggest that the ground dimer-ion electronic state is of rectangular rather than trans-planar geometry.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Publication Date: 1988-05-01
    Print ISSN: 0002-7863
    Electronic ISSN: 1520-5126
    Topics: Chemistry and Pharmacology
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