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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 106 (1997), S. 8981-8994 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The resonance Raman spectrum of InP nanocrystals is characterized by features ascribable to both longitudinal (LO) and transverse (TO) optical modes. The intensity ratio of these modes exhibits a strong size dependence. To calculate the size dependence of the LO and TO Raman cross sections, we combine existing models of Raman scattering, the size dependence of electronic and vibrational structure, and electron vibration coupling in solids. For nanocrystals with a radius 〉10 Å, both the LO and TO coupling strengths increase with increasing radius. This, together with an experimentally observed increase in the electronic dephasing rate with decreasing size, allows us to account for the observed ratio of LO/TO Raman intensities. © 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 88 (1988), S. 220-230 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The laser-induced fragmentation behavior of positive carbon cluster ions has been investigated by tandem time-of-flight techniques for the jet-cooled clusters up to 80 atoms in size. Two distinct photophysical regimes were found. The first applies to clusters with 34 atoms or more, all of which dissociate to produce even numbered fragments. Large even clusters fragment by the loss of the high energy species C2, odd ones lose a C atom. The second regime applies to clusters composed of 31 or less atoms, all of which fragment by the loss of C3. These two regimes are sharply separated by C+32 which fragments to produce small cluster ions in the 10–19 atom size range. Fragmentation of the large clusters occurs on a microsecond or faster time scale only at very high levels of excitation (〉12.8 eV). These photophysical results are interpreted as consequences of the large even clusters having edgeless, spheroidal cage structures while the small ones have linear chain or ring structures.
    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 83 (1985), S. 2293-2304 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Reactions on the surface of a variety of transition metal clusters have been studied in the gas phase at near room temperature using a newly developed fast-flow reaction device. Initial examples of the use of this device are provided by survey studies of the reactivity of iron, cobalt, nickel, copper, and niobium clusters in contact with low concentrations of D2, N2 and CO. Dissociative chemisorption of D2 is found to occur with dramatic sensitivity to cluster size in the cases of iron, cobalt, and niobium clusters, the detailed pattern of reactivity differing markedly for each metal. The corresponding reaction is also observed with nickel clusters, but here the reactivity shows only a slow, steady increase with cluster size. Copper clusters are found to be completely unreactive to H2 chemisorption under these conditions. Molecular nitrogen is found to chemisorb readily to clusters of cobalt and niobium, with a reactivity pattern very similar to that observed with D2. Iron clusters are found to show slight reactivity with N2; only a small amount of chemisorption is observed on the most reactive clusters at high N2 concentration, but the pattern of this reactivity with cluster size is consistent with that observed in D2 chemisorption. In contrast to these highly structured reactivity patterns of D2 and N2, carbon monoxide is found to show only a slow, monotonic increase in reactivity with cluster size. It is suggested that these dramatic reactivity patterns for chemisorption on metal clusters provide stringent tests for future theories as to the nature of chemisorption on metal surfaces at a detailed, molecular level.
    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 83 (1985), S. 5520-5526 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Supersonic beams of clusters of Si and Ge atoms have been produced by laser vaporization followed by supersonic expansion in a helium carrier. The cluster beams were characterized by F2(7.9 eV) and ArF(6.4 eV) excimer laser ionization accompanied by time-of-flight mass analysis. In addition, the feasibility of a resonant two-photon ionization (R2PI) spectroscopic study was explored by two-color experiments involving initial excitation with the second (2.36 eV) and third (3.54 eV) harmonics of the Nd:YAG followed by excimer laser ionization. All two-photon ionization processes were found to produce extensive fragmentation of the larger clusters. The observed fragmentation pattern for the silicon and germanium clusters were remarkably similar to each other, but drastically different from that seen for metal clusters in the same apparatus. Unlike metal clusters, which tend to lose one atom at a time, these semiconductor clusters appear to fragment by a fission process, the daughter ions falling almost exclusively in the size range from 6 to 11 atoms. Time delay studies in the two-color experiments established that clusters of both Si and Ge have excited electronic states with lifetimes of approximately 100 ns. This again is dramatically different from the behavior found with metal clusters, and indicates the feasibility of R2PI spectroscopy on these cold semiconductor particles. The existence of such long-lived excited states indicates that there is probably an energy gap between the band of electronic states being excited and the ground electronic state.
    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 84 (1986), S. 4074-4079 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Supersonic beams of semiconductor clusters with the formula GaxAsy were generated by laser vaporization of a disc of pure GaAs mounted on the side of a pulsed supersonic nozzle. These cluster beams were characterized by laser photoionization with various fixed-frequency lasers followed by time-of-flight mass spectrometry. Mass analysis of the clusters with x+y〉10 showed all clusters in the composition range from Gax+y through GaxAsy to Asx+y to be present in roughly the amount expected from a binomial distribution. In the smaller clusters strong variations were observed from this expected binomial distirbution as a result of kinetic effects in the cluster formation process. Photoionization with an ArF excimer laser at very low pulse energy revealed a pronounced even/odd alternation in the photoionization cross section of the GaxAsy clusters, depending only on the total number of atoms in the cluster. Clusters in the 5–21 atom range with an odd number of atoms were one-photon ionized by the 6.4 eV ArF excimer laser photons. This even/odd alternation in ionization properties of the clusters supports the view that the even clusters have fully paired singlet ground states with no dangling bonds. At higher ArF excimer laser fluences, the observed mass spectrum became increasingly affected by fragmentation. As is true with bulk GaAs surfaces, these GaxAsy clusters evaporate largely by the loss of arsenic (probably As2) when heated by the laser, leaving behind clusters which are richer in gallium.
    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 94 (1991), S. 3271-3273 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The first infrared spectrum of gas phase, jet-cooled C4 has been measured by high resolution diode laser absorption spectroscopy. Twelve rovibrational transitions are assigned to the ν3(σu) antisymmetric stretch of linear 3Σ−g C4. No evidence is observed for the bent structure of triplet C4 recently observed in a matrix study by Cheung and Graham [J. Chem. Phys. 91, 6664 (1989)]. Indeed, the measured band origin (1548.9368(21) cm−1) and effective ground state C–C bond length [1.304 31(21)A] are consistent with several ab initio predictions of a rigid, linear, cumulenic structure for this cluster radical.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 8392-8394 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The high resolution infrared spectrum of the C9 cluster has been measured in direct absorption by infrared diode laser spectroscopy of a pulsed supersonic carbon cluster jet. Fifty-one rovibrational transitions have been assigned to the ν6 (σu ) antisymmetric stretch fundamental of the 1Σ+9 linear ground state of C9. The measured rotational constant [429.30(50) MHz] is in good agreement with ab initio calculations and indicates an effective bond length of 1.278 68(75) A(ring), consistent with cumulenic bonding in this cluster. Several perturbations are observed in the upper state, and the upper- and lower-state centrifugal distortion constants are observed to be anomolously large, evidencing a high degree of Coriolis mixing of the normal modes.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 1724-1729 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The first characterization of the bending potential of the C7 cluster is reported via the observation of the v=11 and v=20 levels of the ν11(πu) bend as hot bands associated with the ν4(σu) antisymmetric stretch fundamental. The lower state hot band rotational constants are measured to be 1004.4(1.3) and 1123.6(9.0) MHz, constituting a 9.3% and 22% increase over the ground state rotational constant [918.89(41) MHz]. These large increases are strong evidence for extremely large amplitude, anharmonic bending modes in this cluster. In addition, quartic and sextic centrifugal distortion constants determined for the ground and ν4=1 states are found to be anomalously large and negative, evidencing strong perturbations between stretching and bending modes.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of the American Chemical Society 109 (1987), S. 359-363 
    ISSN: 1520-5126
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 90 (1986), S. 525-528 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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