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  • 1
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Two new singlet excited electronic states of the imidogen radical have been characterized through (i) analysis of the two photon resonance enhancements they provide in the wavelength resolved multiphoton ionization spectrum of a 1Δ state NH(ND) radicals and (ii) measurements of the kinetic energy of the photoelectrons accompanying the multiphoton ionization process. The i 1Π state is shown to involve a ...3σ21π1 ion core and a Rydberg electron of mixed 3pσ/3dσ character. The zero-point level of this state in ND exhibits an anomalously large Λ-doubling. Photoelectron kinetic energy release measurements reveal that 2+1 resonance enhanced multiphoton ionization via the j 1Δ state of NH leads to population of a range of v+ vibrational levels in the ground state ion and, importantly, to a substantial population of electronically excited B 2Δ state ions. We conclude that the j 1Δ state of NH(ND) also involves a mixture of configurations, including ...3σ21π13dπ1 and the core excited configuration ...3σ11π23sσ1. All observed vibrational levels of this state in both NH and ND show perturbations, some of which have proved amenable to analysis.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 4657-4665 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Experimental dipole couplings for several isotopically substituted modifications of acetylene dissolved in the nematic liquid crystals 1132 (Merck ZLI 1132), EBBA [N-(4-ethoxybenzylidene)-2, 6-dideutero-4-n-butylaniline] and a 55 wt. % 1132/EBBA mixture are obtained from NMR measurements. The dipolar couplings are calculated using a model for the solvent–solute interaction. The interaction is taken to be of second rank tensorial form and the effects of the coupling between the vibrations and rotations are taken into account. The calculated values are in good agreement with the experimental results although some discrepancies exist. These discrepancies are discussed in terms of a possible contribution to the observed carbon–carbon coupling from the anisotropy in the indirect coupling. The results show that the interaction between the vibrations and rotations of the solute plays an important role in determining the observed couplings and that specific interactions with the liquid crystal need not be invoked to explain the results. Previous studies have shown that molecular hydrogen experiences an external electric field gradient due to its liquid crystal environment and that in 55 wt. % 1132/EBBA the value of this field gradient is zero at 301.4 K. It has also been shown that the interaction between this field gradient and the solute molecular quadrupole moment dominates the ordering of molecular hydrogen in liquid crystals, such as 1132 and EBBA, where the field gradient is large. A qualitative analysis indicates that this interaction is important for the ordering of acetylene and that other mechanisms also play a role.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 7634-7639 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: A (2+1) resonance-enhanced multiphoton ionization–photoelectron spectroscopy (REMPI-PES) study of the OH radical has been carried out in the two-photon energy region between 81 300 and 88 900 cm−1. Translationally and rotationally hot OH radicals are generated via photodissociation of hydrogen peroxide or formic acid. The known D 2Σ− (v'=0–2) and hitherto unobserved 3 2Σ−(v'=0) intermediate states in this region (at 81 815.8 and 87 643.7 cm−1 above the ground state) are shown to possess predominant Rydberg character. From the rotational structure in the REMPI spectrum physical parameters have been derived for these states.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 211-221 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Results of combined theoretical and experimental studies of photoelectron spectra resulting from (2+1) resonance enhanced multiphoton ionization (REMPI) via the f 1Π(3pσ), g 1Δ(3pπ), and h 1Σ+(3pπ) Rydberg states of NH are reported. The overall agreement between these calculated and measured spectra is encouraging. Strong ΔN=N+−N'=even peaks, particularly for ΔN=0, are observed in these spectra. Low-energy Cooper minima are predicted to occur in the l=2 wave of the kπ(1Σ+), kπ(1Σ−), and kπ(1Δ) photoelectron channels for the f state, the kπ(1Δ), kδ(1Π), and kδ(1Φ) channels for the g state, and the kπ(1Σ+) and kδ(1Π) channels for the h state of NH. Depletion of the d wave (l=2) contributions to the photoelectron matrix element in the vicinity of these Cooper minima subsequently enhances the relative importance of the odd l waves. The observed ΔN transitions are also affected by strong l mixing in the electronic continuum induced by the nonspherical molecular potential. Interference of continuum waves between degenerate ionization channels also determines the spectral pattern observed for photoionization of the f 1Π state of NH. Photoelectron angular distributions and the angular momentum compositions of photoelectron matrix elements provide further insight into the origin of these Cooper minima.
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  • 5
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 714-716 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: We have measured rotationally resolved photoelectron spectra of the OH radical using (2+1) resonance enhanced multiphoton ionization spectroscopy via the D 2Σ−(3pσ) and 3 2Σ−(4sσ) Rydberg states. For the D 2Σ−(3pσ) state, we observe primarily ΔN=even distributions of ionic rotational states, in contrast to the ΔN=odd distribution expected for ionization of a 3pσ Rydberg electron. The observations are described quantitatively by ab initio calculations which predict a Cooper minimum in the 3pσ→kπ(l=2) channel, whose occurrence determines the ΔN=even ion rotational distribution. In contrast, the 3 2Σ−(4sσ) photoelectron spectra reveal a broad distribution in rotational levels, arising from greater l mixing in the higher Rydberg orbital and much weaker Cooper minima in the continuum.
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 6042-6051 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Kinetic energy resolved electron detection is used to study resonance enhanced multiphoton ionization and dissociation of molecular chlorine via the 2 1∏g Rydberg state. In the two-photon energy region between 63 000 and 73 600 cm−1, a long vibrational progression up to v'=15 associated with this intermediate gerade Rydberg state is observed. The regularity and magnitude of the vibrational spacing indicate that the 2 1∏g state, converging to the ionic ground state, has virtually unperturbed Rydberg character. However, the molecular signals in the photoelectron spectra show strong deviations from Franck–Condon behavior. In addition, intense electron signals arising from one-photon ionization of excited chlorine atoms are observed. An interpretation in terms of a competition between electronic autoionization and dissociation from core-excited molecular Rydberg states situated above the lowest ionization energy is presented. Some of the excited atomic states observed are indicative for Rydberg–Rydberg interactions at large internuclear distances in the dissociation channel.
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 3252-3261 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: In this paper, we report the first rotationally resolved one- and two-color resonance enhanced multiphoton ionization photoelectron spectroscopy (REMPI-PES) study of the HCl molecule. The agreement between our experimental branching ratios and theoretical investigations is excellent. We also report the first zero kinetic energy pulsed field ionization (ZEKE-PFI) experiments carried out in a "magnetic bottle'' electron spectrometer. A direct comparison is made between ZEKE-PFI and REMPI-PES spectra for ionization via several rotational levels of the F 1Δ2(v'=0) and f 3Δ2(v'=0) Rydberg states of HCl. Large differences in both the spin–orbit and rotational branching ratios are found between the ZEKE-PFI and REMPI-PES spectra. These differences can be understood qualitatively on the basis of rotational and spin–orbit autoionization mechanisms.
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  • 8
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 836-853 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: Rydberg states of methyl iodide have been investigated using resonance enhanced multiphoton ionization in combination with photoelectron spectroscopy with nanosecond and picosecond laser pulses. The study of the ns (6≤n≤10) Rydberg states in two-, three-, and four-photon excitations has resulted in an unambiguous identification of state [1] in the 7s and 8s Rydberg states. As a consequence, it is concluded that the transition to 6s[1] in two- and three-photon excitations is anomalously weak. The application of photoelectron spectroscopy to identify the electronic and vibrational nature of a resonance has led to a major reinterpretation of the excitation spectrum of the 6p Rydberg state in two-photon excitation. In many of the recorded photoelectron spectra anomalous electrons are observed, which derive from a one-photon ionization process. This process is suggested to find its origin in the mixing of 6p and 7s character into higher-lying Rydberg states. The major difference between resonance enhanced multiphoton ionization photoelectron spectroscopy with nanosecond and picosecond lasers is found in a less effective dissociation of the molecule in the picosecond experiments.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 5061-5070 
    ISSN: 1089-7690
    Quelle: AIP Digital Archive
    Thema: Physik , Chemie und Pharmazie
    Notizen: The three-photon excitations of the C 1Σ+ and E 1Π states have been investigated with resonance enhanced multiphoton ionization spectroscopy as a function of the polarization of the excitation light. From the observed polarization dependence the contributions of the various excitation routes have been determined, and the electronic character of these states has been analyzed. The results indicate that the v'=0 and 1 vibrational levels of the E 1Π state have slightly different electronic characters.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    Woodbury, NY : American Institute of Physics (AIP)
    Applied Physics Letters 71 (1997), S. 2340-2342 
    ISSN: 1077-3118
    Quelle: AIP Digital Archive
    Thema: Physik
    Notizen: A very small amount of pre-deposited C on a Si substrate causes island formation after epitaxial growth of less than 2 monolayers Ge. These C-induced Ge dots can be as small as 10 nm in lateral size and 1 nm in height. Their areal density is 1011 cm−2. Intense photoluminescence signal from these small Ge quantum dots is observed reaching a maximum for 2.1±0.3 monolayers of Ge. In the initial stages of island formation, the optical transition of the wetting layer is blue-shifted by strain compensation effects. We propose spatially indirect mechanisms of radiative recombination between electrons confined in the underlying wetting layer and holes confined in the Ge islands. © 1997 American Institute of Physics.
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