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  • American Institute of Physics (AIP)  (4)
  • Nature Publishing Group
  • Wiley
  • 1990-1994  (4)
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Year
  • 1
    Electronic Resource
    Electronic Resource
    Vibrational spectra of aniline–Arn van der Waals cations (n=1 and 2) observed by two-color "threshold photoelectron'' [zero kinetic energy (ZEKE)-photoelectron] spectroscopy (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 6399-6406 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Measurements of mass-selected ion-current and threshold photoelectron spectra of jet-cooled aniline–Arn van der Waals complexes (n=1 and 2) have been carried out with a two-color resonantly enhanced multiphoton ionization (REMPI) technique using a high-resolution threshold photoelectron analyzer developed in this laboratory. From our (1+1') REMPI experiments via the respective excited S1 states, we have obtained photoelectron spectra with well-resolved vibrational progressions due to "low-frequency van der Waals modes'' of the cations; νvdW=16 cm−1 (n=1) and νvdW=11 cm−1 (n=2). From Franck–Condon calculations, we have assigned these low-frequency vibrations to the "van der Waals bending'' of the cations. We have also found that the angles of the van der Waals bonds in the cations are changed by 8.2 (n=1) and 8.8 (n=2) degrees with respect to the S1 states. The adiabatic ionization potentials (Ia) of aniline and the aniline–Arn complexes (n=1 and 2) have been determined as 62 268±4 cm−1 (aniline), 62 157±4 cm−1 (n=1), and 62 049±4 cm−1 (n=2). Their shifts ΔIa are 111 cm−1 (n=1) and 219 cm−1 (n=2) with respect to aniline. Spectral shifts due to complex formation have been observed for a total of 13 ring modes of the cations.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.462634
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  • 2
    Electronic Resource
    Electronic Resource
    Absence of photoelectron spectroscopic evidence for "proton tunneling'' in the cation ground state of jet-cooled tropolone (1991)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 9401-9403 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: From our high resolution REMPI threshold photoelectron measurements of jet-cooled tropolone, it has been found that no spectral doublet showing "proton tunneling'' in the cation ground state (D0) is observed within an experimental accuracy of 2 cm−1. The adiabatic ionization potential was obtained as Ia=68 365±5 cm−1.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.461168
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  • 3
    Electronic Resource
    Electronic Resource
    A study of phenylacetylene and styrene, and their argon complexes PA–Ar and ST–Ar with laser threshold photoelectron spectroscopy (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 8926-8933 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In this work, the molecules styrene (ST) and phenylacetylene (PA), as well as their argon complexes ST–Ar and PA–Ar, have been investigated with (1+1') resonance enhanced multiphoton ionization (REMPI) threshold photoelectron spectroscopy (TES). The first adiabatic ionization energies of ST, PA, ST–Ar, and PA–Ar have been measured as 68 267±5, 71 175±5, 68 151±5, and 71 027±5 cm−1, respectively. For both ST–Ar and PA–Ar, the first photoelectron band shows structure in the lowest frequency van der Waals (vdW) bending mode in the ground ionic state, with νvdW being measured as 15 cm−1 in each case. For each molecule excitation to a particular vibrational level of the S1 state followed by ionization, allows structure in that mode to be observed in the threshold photoelectron spectrum. This has been achieved for three modes in both styrene and phenylacetylene. The experimental ionic vibrational frequencies thus obtained, have been compared with those known for the S0 and S1 states.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.463367
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  • 4
    Electronic Resource
    Electronic Resource
    The role of electronic and geometric factors in "proton tunneling:'' A comparative study of tropolone and 9-hydroxyphenalenone by threshold photoelectron spectroscopy (1993)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 56-66 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: High resolution two-color threshold photoelectron spectra of tropolone and 9-hydroxyphenalenone (9-HPO) isolated in a free jet expansion have been measured to study the proton tunneling phenomena in the cation ground state (D0). The tunneling splitting widths of the D0 zeroth vibrational level for the both molecules lie within our experimental accuracy (2 cm−1), indicating that the proton tunneling is inhibited when compared to that obtained in their respective neutral states. By means of a comparative study of these two molecules, the tunneling inhibition has been explained in terms of a large contribution from the electronic factor which represents the changes in charge distribution of the π electrons upon ionization. The geometric factor, which is associated with the ring planarity is less important in determining the rate of tunneling in the D0 state. In the case of tropolone, we have found that the measurement of an out-of-plane skeletal vibration in various electronic states make it possible to describe the tunneling path at a higher level than a simple one-dimensional description. Moreover, the adiabatic ionization energies of 9-HPO and the deuterated 9-HPO have been determined accurately to be 65 338±5 cm−1 (8.1009±0.0006 eV) and 65 350±5 cm−1 (8.1024±0.0006 eV), respectively.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.465783
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